CN108371955B - Sapo-34/zsm-5@高岭土微球复合催化材料及制备和应用 - Google Patents
Sapo-34/zsm-5@高岭土微球复合催化材料及制备和应用 Download PDFInfo
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- CN108371955B CN108371955B CN201810063196.7A CN201810063196A CN108371955B CN 108371955 B CN108371955 B CN 108371955B CN 201810063196 A CN201810063196 A CN 201810063196A CN 108371955 B CN108371955 B CN 108371955B
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- kaolin
- zsm
- sapo
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- molecular sieve
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- 239000004005 microsphere Substances 0.000 title claims abstract description 95
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 91
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 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 abstract description 82
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 73
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 72
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- 239000003054 catalyst Substances 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
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- 238000002425 crystallisation Methods 0.000 claims description 24
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
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- 238000004519 manufacturing process Methods 0.000 claims description 5
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- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
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- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
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- 235000019353 potassium silicate Nutrition 0.000 claims description 3
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 2
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- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 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
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
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Abstract
本发明提供了一种SAPO‑34/ZSM‑5@高岭土微球复合催化材料及其制备和应用,所述方法包括如下步骤:(1)将高岭土制备成高岭土微球,并焙烧得到活化的高岭土微球;(2)将步骤(1)得到的活化的高岭土微球、水、磷源和模板剂混合制备凝胶;(3)将步骤(2)得到的凝胶与ZSM‑5分子筛混合后老化,然后晶化并分离得到SAPO‑34/ZSM‑5@高岭土复合材料;(4)将步骤(3)得到的复合材料进行铵交换处理,焙烧后得到所述SAPO‑34/ZSM‑5@高岭土微球复合催化剂材料。本发明方法不仅大大缩短了催化剂的制备路径,降低了催化剂制备成本;而且可以通过调变合成条件来调变复合材料中SAPO‑34和ZSM‑5分子筛的比例。
Description
技术领域
本发明涉及化工领域,具体的说,本发明涉及一种SAPO-34/ZSM-5@高岭土微球复合催化材料及其制备和应用。
背景技术
随着世界经济的发展,人类对乙烯、丙烯等低碳烯烃的需求量越来越大。而目前乙烯、丙烯的生产还严重依赖于石油,如我国乙烯的60%均来自于石脑油蒸汽裂解,而丙烯也主要来自于石脑油蒸汽裂解和催化裂化(FCC)过程副产。随着石油资源的过度开采,石油的存储量和供应量势必日渐减少。因此以煤或天然气为原料,经甲醇或二甲醚制备低碳烯烃的路线,即甲醇制烯烃(MTO)或甲醇制丙烯(MTP)工艺路线,是目前最有希望替代石脑油路线制备乙烯、丙烯等低碳烯烃的工艺路线。而目前,MTO所用的催化剂的主活性组分是磷酸铝分子筛SAPO-34,MTP所用催化剂的主活性组分是ZSM-5分子筛。由于两种分子筛的酸性和孔道结构的不同,因而分别用于甲醇转化工艺中生产乙烯和丙烯。
SAPO-34分子筛是一种基于硅、磷、铝的分子筛,它是由美国联合碳化物公司(Union Carbide)开发成功(USP4440871),具有菱沸石型(CHA)兼具八元环和四元环的孔道结构,这些结构相连形成笼,有效孔径为0.43-0.50nm。ZSM-5沸石分子筛是美国Mobil公司于20世纪70年代开发的高硅二维直孔道结构沸石,为MFI型拓扑结构,属于正交晶系,由TO4(T=Si、Al、Fe等)四面体连接而成。
虽然SAPO-34和ZSM-5具有良好的催化甲醇转化制取低碳烯烃的催化性能,但目前工业上所用的MTO或MTP催化剂,大多数是采用“半合成”的方法制备,该方法是由化学合成的分子筛与水、基质、粘结剂等混合、搅拌、打浆、干燥、成型等步骤制备而成。这种半合成方法制备的催化剂具有活性组分分布不均匀,粘结剂堵塞孔道等缺点。
发明内容
本发明的一个目的在于提供一种SAPO-34/ZSM-5@高岭土微球复合催化材料的制备方法;本发明采用高岭土微球为原料提供SAPO-34分子筛合成的全部硅铝源,并作为分子筛生长的基质,补充磷源,并在合成过程中加入ZSM-5分子筛的干粉,原位晶化而实现。
本发明的另一目的在于提供一种SAPO-34/ZSM-5@高岭土微球复合催化材料。
本发明的再一目的在于提供一种甲醇制烯烃的方法。
为达上述目的,一方面,本发明提供了一种SAPO-34/ZSM-5@高岭土微球分子筛的制备方法,其中,所述方法包括如下步骤:
(1)将高岭土制备成高岭土微球,并焙烧得到活化的高岭土微球;
(2)将步骤(1)得到的活化的高岭土微球、水、磷源和模板剂混合制备凝胶;
(3)将步骤(2)得到的凝胶与ZSM-5分子筛混合后老化,然后晶化并分离得到SAPO-34/ZSM-5@高岭土复合材料;
(4)将步骤(3)得到的复合材料进行铵交换处理,焙烧后得到所述SAPO-34/ZSM-5@高岭土微球复合催化材料。
本发明方法是利用高岭土中的硅、铝源作为合成SAPO-34分子筛的原料之一,补充磷源,并利用ZSM-5分子筛干粉作为晶种,合成SAPO-34/ZSM-5@高岭土微球复合材料。采用本方法以高岭土中的硅铝组分作为合成SAPO-34分子筛的原料,可以降低合成成本,且所合成的SAPO-34分子筛和ZSM-5分子筛均匀分布在高岭土微球表面。
本发明所述的高岭土提供的硅、铝源是指高岭土微球经过焙烧处理后,可以被盐酸或NaOH溶液抽提出来,进入反应物凝胶,作为分子筛合成的硅铝物种的部分。
根据本发明的制备方法,步骤(1)所述高岭土微球可以按照现有技术常规方法进行制备,而根据本发明一些具体实施方案,其中,步骤(1)为采用喷雾干燥的方法制备高岭土微球。
根据本发明一些具体实施方案,其中,步骤(1)为将高岭土与水和粘结剂混合后,采用喷雾干燥的方法制备高岭土微球。
所述粘结剂可以为本领域常规使用的粘结剂,而根据本发明一些具体实施方案,其中,步骤(1)所述粘结剂为水玻璃、铝溶胶和硅溶胶中的一种或多种的混合物。
根据本发明一些具体实施方案,其中,步骤(1)的高岭土与粘结剂质量比为1.5-2.75。
根据本发明一些具体实施方案,其中,步骤(1)为先将高岭土粉碎、筛分,然后再和水和粘结剂混合。
根据本发明一些具体实施方案,其中,步骤(1)的焙烧温度为650-900℃;优选为750-800℃。
根据本发明一些具体实施方案,其中,步骤(1)的焙烧时间为1-6h;优选为3-4h。
根据本发明的制备方法,步骤(1)所述高岭土微球可以按照现有技术常规高岭土微球尺寸进行制备,而根据本发明一些具体实施方案,其中,步骤(1)中微球的粒径为80-100μm。
根据本发明一些具体实施方案,其中,步骤(2)中各组分摩尔比满足如下条件:(4-6)R:(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(2.0-3.1)P2O5:(111-222)H2O,其中R为模板剂。
其中,铝源和硅源均来自高岭土微球。
根据本发明一些具体实施方案,其中,步骤(2)包括先将磷源与部分水混合均匀,然后加入模板剂,并加入剩余的水,混合均匀后加入步骤(1)得到的活化的高岭土微球,混合均匀得到凝胶。
步骤(2)中活化高岭土微球与模板剂、磷源和水的加料顺序为水-磷源-模板剂-水-高岭土微球
根据本发明一些具体实施方案,其中,步骤(2)所述模板剂选自三乙胺、二乙胺和四乙基氢氧化铵中的一种或多种的混合。
根据本发明一些具体实施方案,其中,步骤(2)所述的磷源为磷酸。
根据本发明一些具体实施方案,其中,步骤(3)中ZSM-5分子筛与凝胶的质量比为0.042-0.066。
根据本发明一些具体实施方案,其中,步骤(3)所述ZSM-5分子筛为未脱模的ZSM-5分子筛。
本发明步骤(3)保留ZSM-5模板剂,可以在原位晶化过程中促进ZSM-5的生成。
根据本发明一些具体实施方案,其中,步骤(3)所述ZSM-5分子筛的硅铝摩尔比为50-200;优选为50-150。
根据本发明一些具体实施方案,其中,步骤(3)老化的温度为40-90℃;优选为70℃。
根据本发明一些具体实施方案,其中,步骤(3)老化的时间为15-60min;优选为30min。
根据本发明一些具体实施方案,其中,步骤(3)晶化的温度为180-220℃。
根据本发明一些具体实施方案,其中,步骤(3))晶化的温度为200℃。
根据本发明一些具体实施方案,其中,步骤(3)晶化的时间为24-72h。
根据本发明一些具体实施方案,其中,步骤(3)晶化的时间为48h。
根据本发明一些具体实施方案,其中,步骤(3)的晶化是在180-220℃下晶化24-72h。
根据本发明一些具体实施方案,其中,步骤(3)的晶化是在200℃下晶化48h。
根据本发明一些具体实施方案,其中,步骤(3)在晶化后,经过包括静置沉淀、离心、洗涤和干燥的步骤得到所述SAPO-34/ZSM-5@高岭土复合材料。
根据本发明一些具体实施方案,其中,步骤(3)是静置沉淀5-15min。
根据本发明一些具体实施方案,其中,步骤(3)干燥的温度为100-120℃,干燥时间为4-12h。
根据本发明一些具体实施方案,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中进行铵交换处理,焙烧后得到所述SAPO-34/ZSM-5@高岭土微球复合催化材料。
根据本发明一些具体实施方案,其中,步骤(4)的氯化铵水溶液摩尔浓度为0.1-1;优选为0.8M。
根据本发明一些具体实施方案,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,在60-90℃条件下搅拌2-6h。
根据本发明一些具体实施方案,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,在80℃条件下搅拌。
根据本发明一些具体实施方案,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,搅拌4h。
根据本发明一些具体实施方案,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,在80℃条件下搅拌4h。
根据本发明一些具体实施方案,其中,步骤(4)的焙烧温度为500-600℃。
根据本发明一些具体实施方案,其中,步骤(4)的焙烧温度为550℃。
根据本发明一些具体实施方案,其中,步骤(4)焙烧时间为3-6h。
根据本发明一些具体实施方案,其中,步骤(4)焙烧时间为4h。
根据本发明一些具体实施方案,其中,步骤(4)的焙烧是在550℃焙烧4h。
另一方面,本发明还提供了本发明所述的制备方法制备得到的SAPO-34/ZSM-5@高岭土微球复合催化材料。
根据本发明一些具体实施方案,其中,以相对结晶度计,其中SAPO-34分子筛的相对含量为7-15wt.%,ZSM-5分子筛的相对含量为6-12wt.%。
再一方面,本发明还提供了一种甲醇制烯烃的方法,其中,所述方法是以甲醇水溶液为原料,以本发明所述的SAPO-34/ZSM-5@高岭土微球复合催化材料为催化剂制备烯烃。
根据本发明一些具体实施方案,其中,所述甲醇水溶液浓度为90-99wt.%,优选为95wt.%。
根据本发明一些具体实施方案,其中,所述方法是以甲醇水溶液为原料,以本发明所述的SAPO-34/ZSM-5@高岭土微球复合催化材料为催化剂,在常压下、反应温度为400-500℃,质量空速为2-3h-1条件下制备烯烃。
根据本发明一些具体实施方案,其中,反应温度为450℃。
根据本发明一些具体实施方案,其中,质量空速为2.5h-1。
根据本发明一些具体实施方案,其中,所述方法是以甲醇水溶液为原料,以本发明所述的SAPO-34/ZSM-5@高岭土微球复合催化材料为催化剂,在常压下、反应温度为450℃,质量空速为2.5h-1条件下制备烯烃。
综上所述,本发明提供了一种SAPO-34/ZSM-5@高岭土微球分子筛及其制备和应用。本发明的方案具有如下优点:
本发明利用高岭土微球同时作为基质和一部分原料,提供合成SAPO-34分子筛所需的全部硅源和铝源,并在合成过程中加入ZSM-5分子筛原粉作为晶种,使SAPO-34和ZSM-5原位生长在高岭土微球上,并使SAPO-34和ZSM-5分子筛在高岭土微球表面均匀分布,制备出SAPO-34/ZSM-5@高岭土微球复合材料,该复合材料经铵交换、焙烧后,可以直接作为MTO催化剂,用于MTO反应装置,这不仅大大缩短了催化剂的制备路径,降低了催化剂制备成本;而且可以通过调变合成条件来调变复合材料中SAPO-34和ZSM-5分子筛的比例,进而调变复合材料的酸性和孔结构,避免半合成方法基质或粘结剂堵塞分子筛孔道的弊端,发挥SAPO-34和ZSM-5分子筛的酸性和孔道结构的协同作用,从而提高MTO反应中乙烯和丙烯的选择性。另外,由于ZSM-5分子筛的引入,SAPO-34/ZSM-5@高岭土微球复合催化剂的MTO反应寿命也大大的延长。
附图说明
图1是实施例1所得复合材料的X-射线衍射图(XRD)谱图。
图2的a和b分别是实施例1所得复合材料放大1000倍和10000倍的场发射扫描电镜(FESEM)图片。
图3是实施例2所得复合材料的XRD谱图。
图4是实施例3所得复合材料的XRD谱图。
图5是实施例4所得复合材料的XRD谱图。
图6是实施例5所得复合材料的XRD谱图。
图7是实施例6所得复合材料的XRD谱图。
图8是实施例7所得复合材料的XRD谱图。
图9是对比例1所得复合材料的XRD谱图。
图10的a和b分别是对比例1所得复合材料放大2000倍和20000倍的FESEM照片。
图11是对比例2所得复合材料的XRD谱图。
图12的a和b分别是对比例2所得复合材料放大500倍和10000倍的FESEM照片。
具体实施方式
以下通过具体实施例详细说明本发明的实施过程和产生的有益效果,旨在帮助阅读者更好地理解本发明的实质和特点,不作为对本案可实施范围的限定。
本发明采用X-射线衍射法(XRD)测定样品的晶相结构;采用场发射环境扫描电镜(FESEM)测定样品的晶形晶貌。
本发明提到的复合材料中SAPO-34分子筛和ZSM-5分子筛的含量均以相对结晶度数据推算。相对结晶度,是指原位晶化产物中各分子筛的特征峰与其对应分子筛标样的特征峰的面积和之比,SAPO-34分子筛的特征峰为2θ=9.5°、16.0°、20.5°、31°处的峰,ZSM-5分子筛的特征峰为2θ=22.5-25°处的峰。标样分子筛分别为南开的催化剂生产的常规的微孔SAPO-34分子筛和自制的微孔ZSM-5分子筛,将它们的结晶度定为100%。
【实施例1】
将高岭土100g加水350g及铝溶胶40g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在700℃焙烧4h,备用。
称取4g磷酸与10g水相混合,搅拌30min,搅拌条件下加入4g三乙胺和10g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:4R:0.30SiO2:1.85Al2O3:2P2O5:111H2O;
称取1.5g未脱模的SiO2/Al2O3为200的ZSM-5分子筛干粉,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.045,40℃搅拌30min;
将上述得到的混合液转移到密闭的高压晶化釜中,在180℃转动烘箱中晶化24h;
将产物取出,静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,100℃干燥4h,用0.5M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在80℃条件下搅拌4h),520℃焙烧3h,后得到SAPO-34/ZSM-5@高岭土微球复合催化材料,通过XRD衍射定量,产物中SAPO-34分子筛的重量含量为7%,ZSM-5分子筛的重量含量为9%,复合材料的XRD衍射谱图如图1所示,扫描电镜图如图2所示。
【实施例2】
将高岭土100g加水350g及铝溶胶35g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取5g磷酸与15g水相混合,搅拌30min,搅拌条件下加入5g三乙胺和15g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:5R:0.20SiO2:1.47Al2O3:2.6P2O5:166H2O;
称取2g未脱模的SiO2/Al2O3为80的ZSM-5分子筛干粉,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.044,70℃搅拌30min;
将上述得到的混合液转移到密闭的高压晶化釜中,在200℃转动烘箱中晶化48h;
将产物取出,静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,120℃干燥6h,用1.0M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在75℃条件下搅拌4h),550℃焙烧4h,得到SAPO-34/ZSM-5@高岭土微球复合催化剂,通过XRD衍射定量,产物中SAPO-34分子筛的重量含量为15%,ZSM-5分子筛的重量含量为12%,复合材料的XRD衍射谱图如图3所示。
【实施例3】
将高岭土100g加水350g及铝溶胶52g、硅溶胶15g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在900℃焙烧6h,备用。
称取6g磷酸与20g水相混合,搅拌30min,搅拌条件下加入6g三乙胺和20g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:6R:0.27SiO2:0.58Al2O3:3.0P2O5:222H2O;
称取3.0g脱模的SiO2/Al2O3为100的ZSM-5分子筛干粉,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.053,90℃搅拌60min;
将上述得到的混合液转移到密闭的高压晶化釜中,在220℃转动烘箱中晶化72h;
将产物取出,静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,110℃干燥12h,用0.1M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在60℃条件下搅拌6h),600℃焙烧6h,得到SAPO-34/ZSM-5@高岭土微球复合分子筛,通过XRD衍射定量,产物中SAPO-34分子筛的重量含量为10%,ZSM-5分子筛的重量含量为7.5%,复合材料的XRD衍射谱图如图4所示。
【实施例4】
将高岭土100g加水350g及铝溶胶45g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取5g磷酸与15g水相混合,搅拌30min,搅拌条件下加入5g三乙胺和15g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:5R:0.20SiO2:1.47Al2O3:2.6P2O5:166H2O;
称取2g未脱模的SiO2/Al2O3为50的ZSM-5分子筛,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.044,70℃搅拌30min;
将上述得到的混合液转移到密闭的高压晶化釜中,在200℃转动烘箱中晶化48h;
将产物取出,经静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,105℃干燥8h,用0.6M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在65℃条件下搅拌5h),550℃焙烧4h,得到SAPO-34/ZSM-5@高岭土微球复合分子筛,通过XRD衍射定量,产物中SAPO-34分子筛的重量含量为11%,ZSM-5分子筛的重量含量为6%,复合材料的XRD衍射谱图如图5所示。
【实施例5】
将高岭土100g加水350g及铝溶胶40g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取5g磷酸与15g水相混合,搅拌30min,搅拌条件下加入7.35g四乙基氢氧化铵和15g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:5R:0.20SiO2:1.47Al2O3:2.6P2O5:166H2O;
称取2g脱模的SiO2/Al2O3为50的ZSM-5分子筛,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.042,70℃搅拌30min;
将上述中得到的混合液转移到密闭的高压晶化釜中,在200℃转动烘箱中晶化48h;
将产物取出,经静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,120℃干燥6h,用0.5M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在85℃条件下搅拌2h),550℃焙烧4h,得到SAPO-34/ZSM-5@高岭土微球复合分子筛。该产品的XRD的衍射图与实施例2制得的产品类似,产物中SAPO-34分子筛的重量含量为10%,ZSM-5分子筛的重量含量为7%,复合材料的XRD衍射谱图如图6所示。
【实施例6】
将高岭土100g加水350g及铝溶胶40g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取5g磷酸与15g水相混合,搅拌30min,搅拌条件下加入3.65g二乙胺和15g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:5R:0.20SiO2:1.47Al2O3:2.6P2O5:166H2O;
称取2g未脱模的SiO2/Al2O3为50的ZSM-5分子筛,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.046,70℃搅拌30min;
将上述中得到的混合液转移到密闭的高压晶化釜中,在200℃动态晶化48h;
将产物取出,经静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,120℃干燥6h,用0.5M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在90℃条件下搅拌3h),550℃焙烧4h,得到SAPO-34/ZSM-5@高岭土微球复合分子筛。该产品的XRD的衍射图与实施例2制得的产品类似,产物中SAPO-34分子筛的重量含量为11%,ZSM-5分子筛的重量含量为6.5%,复合材料的XRD衍射谱图如图7所示。
【实施例7】
将高岭土100g加水350g及硅溶胶36g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取5g磷酸与15g水相混合,搅拌30min,搅拌条件下加入1.33g二乙胺和3.67g四乙基氢氧化铵和15g水,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足:5R:0.20SiO2:1.47Al2O3:2.6P2O5:166H2O;
称取2g未脱模的SiO2/Al2O3为60的ZSM-5分子筛,加入上述得到的混合液中,ZSM-5干粉与凝胶的质量比为0.044,70℃搅拌30min;
将上述中得到的混合液转移到密闭的高压晶化釜中,在200℃动态晶化48h;
将产物取出,经静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,120℃干燥6h,用0.5M的氯化铵,对原位产物进行2次铵交换(每次铵交换均为将得到的原位产物在氯化铵水溶液中,在80℃条件下搅拌3h),550℃焙烧4h,得到SAPO-34/ZSM-5@高岭土微球复合分子筛。该产品的XRD的衍射图与实施例2制得的产品类似,产物中SAPO-34分子筛的重量含量为12%,ZSM-5分子筛的重量含量为6.8%,复合材料的XRD衍射谱图如图8所示。
【对比例1】
将高岭土100g加水350g及铝溶胶40g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取5g磷酸与15g水相混合,搅拌30min,搅拌条件下加入15g水和5g三乙胺,继续搅拌,加入5g高岭土微球,静置2h;制备的凝胶中各成分摩尔比满足5R:0.20SiO2:1.47Al2O3:2.6P2O5:166H2O;
将步骤(1)中得到的混合液转移到密闭的高压晶化釜中,在200℃转动烘箱中晶化48h;
将产物取出,静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,120℃干燥12h,550℃焙烧4h,得到SAPO-34@高岭土复合分子筛,通过XRD衍射定量,产物中SAPO-34分子筛的重量含量为30%,复合材料的XRD衍射谱图如图9所示,扫描电镜图如图10所示。
【对比例2】
将高岭土100g加水350g及铝溶胶40g混合均匀,喷雾干燥得到高岭土微球,将高岭土微球在800℃焙烧4h,备用。
称取1.74g四丙基溴化铵与70g水相混合,搅拌30min,继续搅拌,加入5g高岭土微球,15g水玻璃,搅拌均匀;
将上述得到的混合液转移到密闭的高压晶化釜中,在170℃转动烘箱中晶化48h;
将产物取出,经静置沉降5min,除去上层液的非原位产物,将沉淀原位产物离心分离、洗涤,120℃干燥12h,用0.5M的氯化铵,对原位产物进行2次铵交换,焙烧后得到ZSM-5@高岭土复合分子筛,通过XRD衍射定量,产物中ZSM-5分子筛的重量含量为15%,复合材料的XRD衍射谱图如图11所示,扫描电镜图如图12所示。
【对比例3】
将按照对比例1方法合成的SAPO-34/高岭土微球复合分子筛与按照对比例2方法合成的ZSM-5/高岭土微球复合分子筛按照质量比1:1进行物理混合,混合均匀后进行催化活性评价。
实验例1:SAPO-34/ZSM-5@高岭土微球复合催化剂的催化性能
采用小型固定床催化反应评价装置,分别以实施例1-7所制备的SAPO-34/ZSM-5@高岭土复合催化材料,对比例1所制备的SAPO-34@高岭土、对比例2所制备的ZSM-5@高岭土以及对比例3所制备的SAPO-34@高岭土和ZSM-5@高岭土的复合物为催化剂,评价它们的MTO反应催化性能。
其中,评价原料为95wt.%的甲醇水溶液,评价条件为:反应温度450℃,质量空速2.5h-1,载气流速为20ml/min。反应后的产物采用离线气相色谱进行分析,采用北分3420A气相色谱仪,HP PLOT-Q柱,FID检测器进行检测。当甲醇转化率低于98wt.%时,可认为催化剂已失活,此时停止实验,并将该时间点作为催化寿命。产物选择性结果均取甲醇制烯烃反应过程中取样点中的最大值。结果如表1所示。
表1甲醇制烯烃MTO催化性能评价结果
上述实验结果说明,采用本发明方法,可以通过调变合成条件改变所制备的SAPO-34/ZSM-5@高岭土微球复合催化剂中SAPO-34和ZSM-5的相对含量,进而可以调控MTO反应产物中乙烯和丙烯的选择性,同时,相比于SAPO-34@高岭土微球催化剂,本实验合成的产品具有更好的活性稳定性,催化剂寿命延长了700min以上;而相比于ZSM-5@高岭土和ZSM-5@高岭土与SAPO-34@高岭土的机械催化剂来说,本发明所得到的产品,具有更好的乙烯、丙烯、双烯(乙烯+丙烯)以及三烯(乙烯+丙烯+丁烯)的选择性。
Claims (44)
1.一种SAPO-34/ZSM-5@高岭土微球复合催化材料的制备方法,其中,所述方法包括如下步骤:
(1)将高岭土制备成高岭土微球,并焙烧得到活化的高岭土微球;
(2)将步骤(1)得到的活化的高岭土微球、水、磷源和模板剂混合制备凝胶;
(3)将步骤(2)得到的凝胶与ZSM-5分子筛混合后老化,然后晶化并分离得到SAPO-34/ZSM-5@高岭土复合材料;
(4)将步骤(3)得到的复合材料进行铵交换处理,焙烧后得到所述SAPO-34/ZSM-5@高岭土微球复合催化剂材料;
焙烧后得到所述SAPO-34/ZSM-5@高岭土微球复合催化剂材料中,SAPO-34分子筛的相对含量为7-15wt.%,ZSM-5分子筛的相对含量为6-12wt.%。
2.根据权利要求1所述的制备方法,其中,步骤(2)中各组分摩尔比满足如下条件:(4-6)R:(0.20-0.30)SiO2:(0.58-1.85)Al2O3:(2.0-3.1)P2O5:(111-222)H2O,其中R为模板剂。
3.根据权利要求1或2所述的制备方法,其中,ZSM-5分子筛与凝胶的质量比为0.042-0.066;所述ZSM-5分子筛为未脱模的ZSM-5分子筛。
4.根据权利要求1所述的制备方法,其中,步骤(1)包括将高岭土制备成高岭土微球,并焙烧得到活化的高岭土微球。
5.根据权利要求4所述的制备方法,其中,步骤(1)为采用喷雾干燥的方法制备高岭土微球。
6.根据权利要求5所述的制备方法,其中,步骤(1)为将高岭土与水和粘结剂混合后,采用喷雾干燥的方法制备高岭土微球。
7.根据权利要求6所述的制备方法,其中,步骤(1)所述粘结剂为水玻璃、铝溶胶和硅溶胶中的一种或多种的混合。
8.根据权利要求6所述的制备方法,其中,步骤(1)的高岭土与粘结剂质量比为1.5-2.75。
9.根据权利要求6所述的制备方法,其中,步骤(1)为先将高岭土粉碎、筛分,然后再和水和粘结剂混合。
10.根据权利要求4所述的制备方法,其中,步骤(1)的焙烧温度为650-900℃。
11.根据权利要求10所述的制备方法,其中,步骤(1)的焙烧温度为750-800℃。
12.根据权利要求4、10、11中任一项所述的制备方法,其中,步骤(1)的焙烧时间为1-6h。
13.根据权利要求12所述的制备方法,其中,步骤(1)的焙烧时间为3-5h。
14.根据权利要求4所述的制备方法,其中,步骤(1)中微球的粒径为80-100μm。
15.根据权利要求1所述的制备方法,其中,步骤(2)包括先将磷源与部分水混合均匀,然后加入模板剂,并加入剩余的水,混合均匀后加入步骤(1)得到的活化的高岭土微球,混合均匀得到凝胶。
16.根据权利要求1所述的制备方法,其中,所述模板剂选自三乙胺、二乙胺和四乙基氢氧化铵中的一种或多种的混合。
17.根据权利要求1所述的制备方法,其中,所述的磷源为磷酸。
18.根据权利要求1所述的制备方法,其中,步骤(3)包括将步骤(2)得到的凝胶与ZSM-5分子筛混合后老化,然后晶化并分离得到SAPO-34/ZSM-5@高岭土复合材料。
19.根据权利要求18所述的制备方法,其中,所述ZSM-5分子筛的硅铝摩尔比为50-200。
20.根据权利要求19所述的制备方法,其中,所述ZSM-5分子筛的硅铝摩尔比为50-150。
21.根据权利要求18所述的制备方法,其中,步骤(3)老化的温度为40-90℃。
22.根据权利要求21所述的制备方法,其中,步骤(3)老化的温度为70℃。
23.根据权利要求18、21、22中任一项所述的制备方法,其中,步骤(3)老化的时间为15-60min。
24.根据权利要求23所述的制备方法,其中,步骤(3)老化的时间为30min。
25.根据权利要求18所述的制备方法,其中,步骤(3)晶化的温度为180-220℃。
26.根据权利要求25所述的制备方法,其中,步骤(3)晶化的温度为200℃。
27.根据权利要求18、25、26中任一项所述的制备方法,其中,步骤(3)晶化的时间为24-72h。
28.根据权利要求27所述的制备方法,其中,步骤(3)晶化的时间为48h。
29.根据权利要求18所述的制备方法,其中,步骤(3)在晶化后,经过包括静置沉淀、离心、洗涤和干燥的步骤得到所述SAPO-34/ZSM-5@高岭土复合材料。
30.根据权利要求29所述的制备方法,其中,步骤(3)干燥的温度为100-120℃,干燥时间为4-12h。
31.根据权利要求1所述的制备方法,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中进行铵交换处理,干燥后焙烧得到所述SAPO-34/ZSM-5@高岭土微球复合催化材料。
32.根据权利要求31所述的制备方法,其中,步骤(4)的氯化铵水溶液摩尔浓度为0.1-1M。
33.根据权利要求32所述的制备方法,其中,步骤(4)的氯化铵水溶液摩尔浓度为0.8M。
34.根据权利要求31所述的制备方法,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,在60-90℃条件下搅拌2-6h。
35.根据权利要求34所述的制备方法,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,在80℃条件下搅拌。
36.根据权利要求34所述的制备方法,其中,步骤(4)包括将步骤(3)得到的复合材料在氯化铵水溶液中,搅拌4h。
37.根据权利要求1所述的制备方法,其中,步骤(4)的焙烧温度为500-600℃,焙烧时间为3-6h。
38.权利要求1-37任意一项所述的制备方法制备得到的SAPO-34/ZSM-5@高岭土微球复合催化材料,以相对结晶度计,其中SAPO-34分子筛的相对含量为7-15wt.%,ZSM-5分子筛的相对含量为6-12wt.%。
39.一种甲醇制烯烃的方法,其中,所述方法是以甲醇水溶液为原料,以权利要求38所述的SAPO-34/ZSM-5@高岭土微球复合催化材料为催化剂制备烯烃。
40.根据权利要求39所述的甲醇制烯烃的方法,其中,所述甲醇水溶液浓度为90-99wt.%。
41.根据权利要求40所述的甲醇制烯烃的方法,其中,所述甲醇水溶液浓度为95wt.%。
42.根据权利要求39所述的甲醇制烯烃的方法,其中,所述制备烯烃是在常压下、反应温度为400-500℃、质量空速为2-3h-1条件下制备烯烃。
43.根据权利要求42所述的甲醇制烯烃的方法,其中,所述反应温度为450℃。
44.根据权利要求42所述的甲醇制烯烃的方法,其中,所述质量空速为2.5h-1。
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