CN110330028A - 肺泡状多级孔mfi沸石的制备方法及应用 - Google Patents
肺泡状多级孔mfi沸石的制备方法及应用 Download PDFInfo
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 25
- 239000010457 zeolite Substances 0.000 title claims abstract description 25
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 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 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 8
- 150000001412 amines Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 210000004883 areola Anatomy 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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Abstract
本发明涉及分子筛催化领域，更具体说，涉及一种肺泡状多级孔MFI沸石的制备方法。本发明提供了一种制备具有适宜酸量的肺泡状多级孔MFI沸石的方法与应用，可用于高硅、弱酸性、多级孔分子筛催化反应，优选用于甲醇制丙烯反应。本发明肺泡状多级孔MFI沸石总孔容达到1.00cm3/g以上，大幅提高了催化剂的扩散性能，同时为MTP反应引入了适量的酸性位点。本发明得到由许多小空腔构成的肺泡状多级孔ZSM‑5，总孔容达到1.28cm3/g，固体收率高于60％。本发明在甲醇制丙烯反应中，催化寿命是高Si/Al ZSM‑5、普通多级孔ZSM‑5的两倍多，同时丙烯选择性提高4％。
Description
技术领域
本发明涉及分子筛催化领域，更具体说，涉及一种肺泡状多级孔MFI沸石的制备方法。
背景技术
沸石是微孔结晶型材料，具有可调的酸性、优异的孔道择形性和高水热稳定性，在催化及分离等方面有广泛应用。ZSM-5类沸石是甲醇制丙烯(MTP)反应的催化材料，然而其微孔结构容易积炭，导致其在MTP反应中的稳定性较低。如何进一步提高催化剂的稳定性和丙烯选择性是MTP反应面临的重要挑战，其关键在于催化剂的设计。
在沸石中引入介孔或大孔结构，制备多级孔沸石，可显著改善扩散性能。近些年，研究者们开发了许多制备多级孔沸石的方法，主要包括后处理法和模板法。通过碱处理法将介孔结构引入沸石，可以显著提高其在MTP反应中的稳定性和丙烯选择性。碱处理法可直接用于已经工业化生产的催化剂，具有较好的应用前景。优异的MTP催化剂兼具多级孔结构和适宜的酸量。然而适合碱处理造介孔的ZSM-5的Si/Al在25～50左右，处理得到的多级孔ZSM-5酸量较多，导致其丙烯选择性较低。高Si/Al ZSM-5经碱处理后的酸量适宜，但固体收率低于40％，同时碱处理产生大孔结构。通过碱处理法制备高收率且酸量适宜的介孔ZSM-5存在一定挑战。
发明内容
基于以上问题，本发明提供了一种制备具有适宜酸量的肺泡状多级孔MFI沸石的方法，具体操作方法如下：
S1、将四丙基溴化铵TPABr和硅溶胶按比例混合，标记为A；将硼酸、65％质量浓度乙胺水溶液和水按比例混合后，标记为B；
按质量份数，各原料组成为四丙基溴化铵2～20份，硅溶胶20～100份，硼酸0.2～3份，乙胺水溶液10～40份，水20～80份；
S2、将步骤S1制得的A溶液在20～60℃搅拌0～180min后，加入B，在80～240℃条件下，晶化1～240h；离心分离、烘干、焙烧后得到H型B-MFI，标记为BHZ；
优选方式下，步骤S2在晶化前还可以再加入纳米Silicalite-1晶种，混合搅拌0～180min后，进行晶化；所述纳米Silicalite-1晶种按步骤S1中各原料组成质量份数计，加入0～100份；
上述B-MFI沸石为纳米团聚体；
S3、向浓度为0.02～0.5mol/L的NaOH溶液中加入铝制剂，使溶液中Al浓度达到0～0.02mol/L，加热至40～100℃后，将步骤S2制得的BHZ样品粉末迅速倒入NaOH溶液中，所述NaOH溶液与BHZ样品的液固比为5～60mL/g，搅拌2～180min后，冷却至18～22℃，离心分离、洗至中性，烘干，焙烧得到固体粉末，即肺泡状多级孔MFI沸石，经铵交换后得到H型肺泡状多级孔MFI沸石。
步骤S3所述铝制剂优选Al(NO3)3·9H2O、Al2(SO4)3·18H2O、AlCl3·6H2O、Al(OH)3、NaAlO2或Al2O3中的一种或几种混合。
本发明还提供了一种上述具有适宜酸量的肺泡状多级孔MFI沸石的应用，用于高硅、弱酸性、多级孔分子筛催化反应。
优选方式下，用于甲醇制丙烯反应。
相比于现有技术，本发明具有以下优点：
1、本发明通过碱处理纳米团聚体B-MFI加铝制剂的方式得到肺泡状多级孔MFI沸石，总孔容达到1.00cm3/g以上，大幅提高了催化剂的扩散性能，同时为MTP反应引入了适量的酸性位点。
2、本发明采用一步处理法，在碱处理硼硅MFI沸石(B-MFI)纳米团聚体时，加入铝源，可得到由许多小空腔构成的肺泡状多级孔ZSM-5，总孔容达到1.28cm3/g，固体收率高于60％。与Silicalite-1(纯硅MFI沸石)相比，硼的加入有助于NaOH溶液中Al3+插入沸石骨架，成为四配位骨架铝，使肺泡状多级孔ZSM-5具有适宜的酸量。
3、本发明制得的具有适宜酸量的肺泡状多级孔MFI沸石在甲醇制丙烯(MTP)反应中，催化寿命是高Si/Al ZSM-5、普通多级孔ZSM-5的两倍多，同时丙烯选择性提高4％。
附图说明
图1为实施例制得的母体BHZ和不同碱处理方法得到样品的扫描电镜照片：a.BHZ；b.BHZ-AT；c.BHZ-AT-15Al；d.BHZ-AT-30Al；e.BHZ-AT-60Al；f.BHZ-AT-75Al
图2为实施例制得的母体和不同碱处理方法得到样品的透射电镜照片：a.BHZ；b.BHZ-AT；c.BHZ-AT-15Al；d.BHZ-AT-30Al；e.BHZ-AT-60Al；f.BHZ-AT-75Al
图3为应用例中不同催化剂用于MTP反应甲醇转化率随时间变化趋势；
图4为应用例中不同催化剂在MTP反应中产物选择性随时间变化趋势
具体实施方式
实施例
1.将13.34g TPABr和66.67g硅溶胶混合，标记为A；将1.65g硼酸、22.26g乙胺水溶液和45g水混合后，标记为B；A在35℃搅拌30min后，加入B，接着加入2.08g纳米Silicalite-1晶种，混合搅拌90min后，将得到的母液转移至带有聚四氟乙烯内衬的200mL晶化釜中，在170℃晶化72h。母液中各组分的摩尔比为1SiO2:0.04B2O3:0.15TPABr:1C2H5NH2:17H2O。晶化后的悬浊液经离心分离、烘干和焙烧后得到H型B-MFI，标记为BHZ。搅拌完成后，装釜，于170℃下晶化5h。
2.配制浓度为0.2mol/L的NaOH溶液，待在NaOH溶液中加入Al(NO3)3·9H2O，调节Al浓度为0mol/L、0.0015mol/L、0.0030mol/L、0.0045mol/L、0.0060mol/L或0.0075mol/L，其中，0mol/L为不加Al制剂；待溶液温度稳定至80℃后，将BHZ样品粉末迅速倒入NaOH溶液中(液固比为30mL/g)，开始计时，搅拌30min后将烧杯置于冰水浴中冷却。离心分离(洗至接近中性)，烘干，焙烧得到固体粉末，经铵交换后得到H型样品。
本发明主要专注于后处理过程：步骤2处理得到的样品经铵交换后分别标记为BHZ-AT、BHZ-AT-15Al、BHZ-AT-30Al、BHZ-AT-45Al、BHZ-AT-60Al或BHZ-AT-75Al。
在75℃条件下，BHZ-AT-30Al样品经0.2mol/L·HCl处理8h，液固比为30mL/g，酸洗(Acid Washing)后的样品标记为BHZ-AT-30Al-AW。
图1和图2为不同样品的扫描电镜和透射电镜照片，结果显示处理得到的样品具有肺泡状多级孔结构，物理吸附结果如表1所示。结果显示，处理得到的样品的总孔容大幅提升，最大可以达到1.28cm3/g，远高于普通多级孔ZSM-5。
表1不同样品的物化数据统计
对比例
将四丙基溴化铵(TPABr)、纳米Silicalite-1晶种(晶种加入量为0.5wt％，晶种悬浊液中SiO2的质量占投料SiO2质量的0.5％)和硅溶胶(30wt％)混合配成A；将AlCl3·6H2O水中，配成B；将A在35℃搅拌30min后加入B中，继续搅拌90min后，加入乙胺水溶液(65wt％)，搅拌10min后装釜，170℃晶化72h。晶化后的悬浊液经离心分离，烘干，焙烧后得到ZSM-5。配方中各组分摩尔比为SiO2:Al2O3:TPABr:C2H7N:H2O＝1:x:0.20:y:17。当x＝0.0025,y＝0.04时，投料硅铝比为200，得到样品的实测硅铝比为153，标记为Z153；当x＝0.01,y＝0.20时，投料硅铝比为50，得到样品的实测硅铝比为45，标记为Z45；Z45样品经0.2mol/L NaOH溶液在80℃处理30min后得到的样品标记为Z45-AT。
应用例
采用上述实施例及对比例制得的催化剂用于MTP反应。
反应温度：500℃；反应压力：常压；甲醇质量空速：3h-1；催化剂装填量：1g；水醇摩尔比：1：1。
反应结果(图3)显示，通过特殊碱处理法得到的样品BHZ-AT-30Al和BHZ-AT-30Al-AW样品的催化稳定性远高于传统高硅铝比ZSM-5(Z153,Si/Al＝153)和普通多级孔ZSM-5(Z45-AT，Si/Al为45的ZSM-5经NaOH处理得到)，而母体BHZ样品没有反应活性。
图4为不同样品在MTP反应中的产物分布，结果显示BHZ-AT-30Al和BHZ-AT-30Al-AW样品的丙烯选择性大幅提高。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明披露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (5)
1.一种肺泡状多级孔MFI沸石的制备方法，其特征在于，具体操作方法如下：
S1、将四丙基溴化铵TPABr和硅溶胶按比例混合，标记为A；将硼酸、质量浓度为65％乙胺水溶液和水按比例混合后，标记为B；
按质量份数，各原料组成为四丙基溴化铵2～20份，硅溶胶20～100份，硼酸0.2～3份，乙胺水溶液10～40份，水20～80份；
S2、将步骤S1制得的A溶液在20～60℃搅拌0～180min后，加入B，在80～240℃条件下，晶化1～240h；离心分离、烘干、焙烧后得到H型B-MFI，标记为BHZ；
S3、向浓度为0.02～0.5mol/L的NaOH溶液中加入铝制剂，使溶液中Al浓度达到0～0.02mol/L，加热至40～100℃后，将步骤S2制得的BHZ样品粉末迅速倒入NaOH溶液中，所述NaOH溶液与BHZ样品的液固比为5～60mL/g，搅拌2～180min后冷却至18～22℃，离心分离、洗至中性，烘干，焙烧得到固体粉末，即肺泡状多级孔MFI沸石，经铵交换后得到H型肺泡状多级孔MFI沸石。
2.根据权利要求1所述肺泡状多级孔MFI沸石的制备方法，其特征在于，步骤S2在晶化前加入纳米Silicalite-1晶种，混合搅拌0～180min后，进行晶化；
所述纳米Silicalite-1晶种按步骤S1中各原料组成质量份数计，加入0～100份。
3.根据权利要求1所述肺泡状多级孔MFI沸石的制备方法，其特征在于，步骤S3所述铝制剂为Al(NO3)3·9H2O、Al2(SO4)3·18H2O、AlCl3·6H2O、Al(OH)3、NaAlO2或Al2O3中的一种或几种混合。
4.一种权利要求1-3所述方法制得的肺泡状多级孔MFI沸石的应用，其特征在于，用于高硅、弱酸性、多级孔分子筛催化反应。
5.根据权利要求4所述肺泡状多级孔MFI沸石的应用，其特征在于，用于甲醇制丙烯反应。
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