CN114572998A - 一种条形聚集体分子筛及其合成方法和应用 - Google Patents
一种条形聚集体分子筛及其合成方法和应用 Download PDFInfo
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- CN114572998A CN114572998A CN202011293799.XA CN202011293799A CN114572998A CN 114572998 A CN114572998 A CN 114572998A CN 202011293799 A CN202011293799 A CN 202011293799A CN 114572998 A CN114572998 A CN 114572998A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 80
- 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 80
- 238000001308 synthesis method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 230000032683 aging Effects 0.000 claims description 12
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000005728 strengthening Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 235000013024 sodium fluoride Nutrition 0.000 claims description 5
- 239000011775 sodium fluoride Substances 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- 241000269350 Anura Species 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 10
- 239000010457 zeolite Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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Abstract
本发明公开了一种条形聚集体分子筛及其合成方法和应用。本发明提供的条形聚集体分子筛,所述分子筛形貌呈条形聚集体,条形的三维方向平均尺寸分别为600‑1000nm、200‑400nm、100‑200nm,聚集体大小为4‑8μm。该分子筛具有特殊形貌,应用于烯烃裂解反应中,具有良好的催化效果。
Description
技术领域
本发明属于沸石分子筛技术领域,具体为一种条形聚集体形貌分子筛及其合成方法和应用。
背景技术
自19世纪50年代Union Carbide公司成功开发出不同沸石分子筛工业化合成路线之后,具有多变孔道结构的分子筛得到广泛工业化应用。之后,Mobil、Unocal及UnionCarbide公司将微孔沸石分子筛应用于石油化工精制及汽油生产工业中,由于具有孔道结构多样性、稳定独特的选择与择形选择相结合的性能,分子筛催化很快发展成为工业催化领域中的一个专门分支学科,迅速引起人们的关注并逐步在全世界范围内开始使用。
CN201110217559.6公开了一种梯度酸分布ZSM-5分子筛及其制备方法。该方法制备的ZSM-5分子筛氧化硅/氧化铝摩尔比为25-200,同时具备弱酸、强酸以及超强酸。该方法主要是通过对ZSM-5分子筛补加铝源进行二次合成制备得到具有梯度酸分布的ZSM-5分子筛。该方法得到的ZSM-5分子筛产品具有梯度的酸性质,在异构化、烷基化以及催化裂化等领域具有广泛的应用前景。CN201210153420.4介绍了一种中空胶囊状纳米ZSM-5分子筛及制备方法,SiO2/Al2O3摩尔比为30~600,粒径10~600nm,厚度50~200nm,具有0.05~2nm微孔,壁厚1~10nm。制备方法是由碱处理脱硅形成中空结构的胶囊状ZSM-5分子筛,得到分子筛催化剂具有较高的结晶度,分部狭窄、均一的大空腔,空腔可调范围大;分子筛催化剂中同时存在中间大孔和分子筛晶内微孔,克服了沸石分子筛微孔对其催化性能的限制;同时,还可以增加催化剂的比表面积,获得催化反应高转化率。CN201410098297.X涉及一种制备等级结构ZSM-5的方法,具体为酸碱耦合制备等级孔ZSM-5分子筛的方法。步骤为将商业ZSM-5与碱液按照比例混合升温搅拌形成悬浮液,将悬浮液进行过滤,滤饼用水或酸液洗涤,最后再用酸性铵盐溶液进行离子交换,然后焙烧,得到等级孔结构ZSM-5分子筛。该方法旨在制备富二次介孔ZSM-5分子筛,首先通过环境友好化碱处理方式脱除ZSM-5中的部分硅铝物种,制备具有二次孔结构的ZSM-5分子筛;在二次孔已经形成的基础上,然后再通过酸洗或者离子交换的方式,让ZSM-5表面以及滞留在孔道中的无定形结构溶出,同时提高富二次介孔ZSM-5的孔容和比表面积。通过酸碱耦合处理,改善了ZSM-5表面骨架外铝的分布状态,因此该方法制备的富二次介孔ZSM-5在催化裂化、加氢裂化中有很大的应用潜力。CN201210073742.8提供了一种ZSM-5沸石分子筛微球的制备方法,利用含甲基的有机硅氧烷和正硅酸乙酯作硅源一步法制备ZSM-5沸石分子筛微球,微球是由细小的ZSM-5沸石晶粒组成的,改变含甲基硅氧烷的添加量,微球的大小可在3-8μm调节,且ZSM-5沸石分子筛微球尺寸均匀,分散性好,制备过程简单,易于大量制备,可在催化、吸附和分离等方面得到应用。
以上专利所述方法中,模板剂用量较高,所需老化时间和晶化时间依然较长,晶化温度较高,制备分子筛合成过程比较复杂。且无法得到条形分子筛聚集体。
发明内容
本发明所要解决的技术问题之一是提供一种现有技术无法得到的新的条形聚集体分子筛。
本发明所要解决的技术问题之二是针对现有技术使用模板剂用量较高,所需老化时间和晶化时间依然较长,晶化温度较高,制备分子筛合成过程比较复杂的问题,提供一种条形聚集体分子筛的合成方法。
本发明所要解决的技术问题之三提供一种条形聚集体分子筛在烯烃裂解反应中的应用。针对技术问题一,本发明提供了一种条形聚集体分子筛,所述分子筛形貌呈条形聚集体,条形的三维方向平均尺寸分别为600-1000nm、200-400nm、100-200nm,聚集体大小为4-8μm。
上述技术方案中,所述条形的三维方向平均尺寸优选为700-900nm、200-350nm、110-190nm,聚集体大小优选为5-7μm。
上述技术方案中,所述分子筛为ZSM分子筛、X型分子筛、Y型分子筛、Beta分子筛、丝光沸石、SAPO分子筛、MCM分子筛中一种或多种复合分子筛,优选为ZSM-5分子筛。
针对技术问题二,本发明提供了一种条形聚集体分子筛的合成方法,具体包括以下步骤:
(1)将模板剂R及硅源混合配制溶液A,将铝源及辅助剂S配制溶液B;
(2)将溶液A和溶液B同时且分两路通入反应器进行反应,所得产物进行老化处理得到待晶化液体;之后再进行晶化处理,得到条形聚集体分子筛。
上述技术方案中,步骤(1)所述模板剂R为正丙胺、正丁胺、正己胺、甲胺、乙胺、乙二胺、二乙醇胺、丁内酯、戊内酯、己内酯中至少一种。
上述技术方案中,步骤(1)所述辅助剂S为氟化钠、氟化铵中至少一种。
上述技术方案中,步骤(1)所述硅源为硅溶胶、正硅酸乙酯、无定形氧化硅、硅酸盐中至少一种,其中,硅源的SiO2固含量为30%-70%。所述铝源为硫酸铝、异丙醇铝、偏铝酸盐、铝酸盐中至少一种。
上述技术方案中,步骤(1)中溶液A中按物料配比以H2O、有机模板剂R和硅源以SiO2计摩尔比为5-1000:0.1-0.6:1称取定量的模板剂R及硅源配制。
上述技术方案中,步骤(1)中溶液B中铝源与硅源摩尔比为Si/Al=0.5-∞,作为非限定性举例,可以为5、10、20、30、50、100、500、800。
上述技术方案中,步骤(1)中辅助剂S和硅源以SiO2计摩尔比为0.1-1。
上述技术方案中,步骤(2)将步骤(1)中的溶液A和溶液B分两路通入微观过程强化反应釜中,溶液A和溶液B体积流量为N(A):N(B)=0.5-3:1;经停留时间1-10min后,所得产物经老化处理得到待晶化液体。
上述技术方案中,步骤(2)中溶液A和溶液B通入反应器在搅拌下进行,转速为10-3000rpm,优选为1000-2500rpm。
上述技术方案中,步骤(2)中,所述老化的老化时间为10-120min,更优选为10-30min。
上述技术方案中,步骤(2)中,所述晶化的晶化温度为50-140℃,优选为60-120℃。
上述技术方案中,步骤(2)中,所述晶化的晶化时间为30-240min,优选为30-120min。
上述技术方案中,步骤(2)中,所述的晶化过程在10-1000rpm搅拌下进行。
上述技术方案中,在晶化步骤结束之后,可以通过常规已知的任何分离方式从所获得的混合物中分离出分子筛产品。作为所述分离方式,比如可以举出对所述获得的混合物进行过滤、洗涤和干燥的方法。在此,所述过滤、洗涤和干燥可以按照本领域常规已知的任何方式进行。具体举例而言,作为所述过滤,比如可以简单地抽滤所述获得的产物混合物。作为所述洗涤,比如可以举出使用去离子水和/或乙醇进行洗涤。作为所述干燥温度,比如可以举出40~250℃,优选60~150℃,作为所述干燥的时间,比如可以举出8~30小时,优选10~20小时。该干燥可以在常压下进行,也可以在减压下进行。
针对技术问题三,本发明提供了一种条形聚集体分子筛在烯烃裂解反应中的应用,其中烯烃与上述提供的条形聚集体分子筛接触进行催化裂解反应,得到丙烯和丁烯。
在上述技术方案中,所述烯烃为C4-C8的烯烃,反应条件如下:反应温度550-580℃,反应压力0.01-1MPa,体积空速为5-30h-1。
本发明具有如下有益效果:
本发明提供的分子筛具有特殊形貌,为条形聚集体。而且本发明制备条形聚集分子筛的方法,使用模板剂用量较低,所需老化时间和晶化时间短,晶化温度较低,制备分子筛合成过程简单。
本发明提供的条形聚集体分子筛应用于烯烃裂解反应中,具有良好的催化效果。
附图说明
图1是实施例1制得的分子筛XRD衍射图;
图2是实施例1制得的分子筛SEM照片;
图3是比较例1制得的分子筛SEM照片;
图4是比较例2制得的样品XRD衍射图。
具体实施方式
下面通过实施例对本发明的技术方案作进一步阐述,但本发明的保护范围不受实施例的限制。本发明中,wt%为质量分数。
本发明中,样品的扫描电镜(SEM)照片在日立S-4800II型扫描电子显微镜上拍摄;对于样品的三维尺寸为平均值,测定方法为随机选取100个样品测点取得数据后,再取平均值。
本发明中,XRD的测试条件:采用日本理学Rigaku-Ultima型X射线衍射仪进行分子筛晶相分析。CuKα辐射,波长λ=0.15432nm。X射线衍射图谱扫描范围2θ为5-50°,扫描速度10°/min。
【实施例1】
配制物料A:将0.2g正丙胺、6.7g硅溶胶(固含量为50wt%)加入7.5g水中,搅拌均匀。配制物料B:将0.5g氟化钠,0.09g十八水合硫酸铝加入7.5g水中,搅拌均匀。上述物料分两路通入微观过程强化反应釜中,调节转速1500rpm,同时控制物料A及物料B体积流量为N(A):N(B)=1,停留时间为5min,得到待晶化液体。老化30min,之后放入晶化釜中,升温至120℃,150rpm搅拌下晶化2h,反应结束后,冷却至室温,去离子水洗涤离心3次,80℃烘干12h,焙烧,得到最终产品。
样品XRD图见图1,由图1可以看到产品具有ZSM-5特征衍射峰。产品SEM照片见图2,可以看到样品为条形三维方向尺寸约为700nm、200nm、110nm,聚集体大小约为5μm。
【实施例2】
采用和实施例1相同条件,改变氟化钠用量为1.5g,得到最终产品。
实施例2制得到的样品XRD与图1类似,说明具有ZSM-5特征衍射峰。产品SEM照片与图2类似,可以看到样品为条形聚集体。条形三维方向尺寸约为700nm、250nm、110nm,聚集体大小为5μm。
【实施例3】
采用和实施例1相同条件,改变氟化钠用量为2.5g,得到最终产品。
实施例2制得到的样品XRD与图1类似,说明具有ZSM-5特征衍射峰。产品SEM照片与图2类似,可以看到样品为条形聚集体。条形三维方向尺寸约为800nm、300nm、120nm,聚集体大小约为7μm。
【实施例4】
配制物料A:将0.38g正丁胺、6.7g硅溶胶(固含量为50wt%)加入7.5g水中,搅拌均匀。配制物料B:将0.78g氟化铵,0.09g十八水合硫酸铝加入7.5g水中,搅拌均匀。上述物料分两路通入微观过程强化反应釜中,调节转速1500rpm,同时控制物料A及物料B体积流量为N(A):N(B)=1,停留时间为5min,得到待晶化液体。老化30min,之后放入晶化釜中,升温至120℃,150rpm搅拌下晶化2h,反应结束后,冷却至室温,去离子水洗涤离心3次,80℃烘干12h,焙烧,得到最终产品。
实施例4制得到的样品XRD与图1类似,说明具有ZSM-5特征衍射峰。产品SEM照片与图2类似,可以看到样品为条形聚集体。条形三维方向尺寸约为800nm、300nm、120nm,聚集体大小约为7μm。
【实施例5】
配制物料A:将0.5g乙醇胺、10g硅溶胶(固含量为50wt%)加入8.9g水中,搅拌均匀。配制物料B:将0.9g氟化铵,0.09g十八水合硫酸铝加入7.5g水中,搅拌均匀。上述物料分两路通入微观过程强化反应釜中,调节转速1500rpm,同时控制物料A及物料B体积流量为N(A):N(B)=1,停留时间为5min,得到待晶化液体。老化30min,之后放入晶化釜中,升温至120℃,150rpm搅拌下晶化2h,反应结束后,冷却至室温,去离子水洗涤离心3次,80℃烘干12h,焙烧,得到最终产品。
实施例5制得到的样品XRD与图1类似,说明具有ZSM-5特征衍射峰。产品SEM照片与图2类似,可以看到样品为条形聚集体。条形三维方向尺寸约为800nm、300nm、120nm,聚集体大小为6μm。
【比较例1】
不使用辅助剂S,配制物料A:将0.2g正丙胺、6.7g硅溶胶(固含量为50wt%)加入7.5g水中,搅拌均匀。配制物料B:将0.09g十八水合硫酸铝加入7.5g水中,搅拌均匀。上述物料分两路通入微观过程强化反应釜中,调节转速1500rpm,同时控制物料A及物料B体积流量为N(A):N(B)=1,停留时间为5min,得到待晶化液体。老化30min,之后放入晶化釜中,升温至120℃,150rpm搅拌下晶化2h,反应结束后,冷却至室温,去离子水洗涤离心3次,80℃烘干12h,焙烧,得到最终产品。
比较例1制得到的样品XRD与图1类似,说明具有ZSM-5特征衍射峰。所得样品见图3,不是条形聚集体。
【比较例2】
不使用模板剂R,配制物料A:将0.2g正丙胺、6.7g硅溶胶(固含量为50wt%)加入7.5g水中,搅拌均匀。配制物料B:将0.09g十八水合硫酸铝加入7.5g水中,搅拌均匀。上述物料分两路通入微观过程强化反应釜中,调节转速1500rpm,同时控制物料A及物料B体积流量为N(A):N(B)=1,停留时间为5min,得到待晶化液体。老化30min,之后放入晶化釜中,升温至120℃,150rpm搅拌下晶化2h,反应结束后,冷却至室温,去离子水洗涤离心3次,80℃烘干12h,焙烧,得到最终产品。
比较例2所得样品XRD见图4,为无定形。
【实施例6】
将由实施例1制备的条形分子筛聚集体应用于丁烯裂解反应中,催化剂用量0.6g,反应温度550℃时,反应压力0.04MPa,体积空速为10h-1,反应时间6小时后,丁烯转化率为80%,丙烯选择性为45%。
【比较例3】
同实施例6,区别仅在于:将实施例1制备的条形聚集体换成比较例1制备的产品。结果:丁烯转化率为68%,丙烯选择性为30%。
Claims (10)
1.一种条形聚集体分子筛,所述分子筛形貌呈条形聚集体,条形的三维方向平均尺寸分别为600-1000nm、200-400nm、100-200nm,聚集体大小为4-8μm。
2.根据权利要求1所述的条形聚集体分子筛,其特征在于,所述条形的三维方向平均尺寸为700-900nm、200-350nm、110-190nm,聚集体大小为5-7μm。
3.根据权利要求1所述的条形聚集体分子筛,其特征在于,所述分子筛为ZSM分子筛、X型分子筛、Y型分子筛、Beta分子筛、丝光沸石、SAPO分子筛、MCM分子筛中一种或多种复合分子筛,优选为ZSM-5分子筛。
4.一种权利要求1-3任一项所述的条形聚集体分子筛的合成方法,包括以下步骤:
(1)将模板剂R及硅源混合配制溶液A,将铝源及辅助剂S配制溶液B;
(2)将溶液A和溶液B同时且分两路通入反应器进行反应,所得产物进行老化处理得到待晶化液体;之后再进行晶化处理,得到条形聚集体分子筛。
5.根据权利要求4所述的合成方法,其特征在于,步骤(1)所述模板剂R为正丙胺、正丁胺、正己胺、甲胺、乙胺、乙二胺、二乙醇胺、丁内酯、戊内酯、己内酯中至少一种。
6.根据权利要求4所述的合成方法,其特征在于,步骤(1)所述辅助剂S为氟化钠、氟化铵中至少一种。
7.根据权利要求4所述的合成方法,其特征在于,步骤(2)将步骤(1)中的溶液A和溶液B分两路通入微观过程强化反应釜中,溶液A和溶液B体积流量为N(A):N(B)=0.5-3:1;经停留时间1-10min后,所得产物进行老化处理得到待晶化液体。
8.根据权利要求4所述的合成方法,其特征在于,步骤(2)中,所述老化的老化时间为10-120min;所述晶化条件为:晶化温度为50-140℃,晶化时间为30-240min,晶化过程在10-1000rpm搅拌下进行。
9.一种条形聚集体分子筛在烯烃裂解反应中的应用,其特征在于,烯烃与权利要求1-3任一项所述的条形聚集体分子筛接触进行催化裂解反应,得到丙烯和丁烯。
10.根据权利要求9所述的应用,其特征在于,所述烯烃为C4-C8的烯烃;反应条件如下:反应温度550-580℃,反应压力0.01-1MPa,体积空速为5-30h-1。
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CA2359825A1 (en) * | 2000-10-26 | 2002-04-26 | Quanjie Liu | A mesoporous aluminum based molecular sieve and a process for the preparation of the same |
CN105523568A (zh) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | 一维棒状形貌zsm-5分子筛及合成方法 |
CN109678175A (zh) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | 特殊形貌zsm-5分子筛合成方法 |
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CA2359825A1 (en) * | 2000-10-26 | 2002-04-26 | Quanjie Liu | A mesoporous aluminum based molecular sieve and a process for the preparation of the same |
CN105523568A (zh) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | 一维棒状形貌zsm-5分子筛及合成方法 |
CN109678175A (zh) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | 特殊形貌zsm-5分子筛合成方法 |
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