CN107899610A - 一种mto催化剂载体的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 22
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 13
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- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 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 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 150000003053 piperidines Chemical class 0.000 claims description 6
- -1 polyethylene Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- 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 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 3
- 238000004064 recycling Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- 229910021641 deionized water Inorganic materials 0.000 description 6
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- B01J29/80—Mixtures of different zeolites
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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- C—CHEMISTRY; METALLURGY
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- 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
- B01J29/42—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 containing iron group metals, noble metals or copper
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Abstract
本发明的目的是提供一种MTO催化剂载体的制备方法。具体步骤如下：制备纳米改性复合粉体，取铝源、磷源、水、ZSM‑5原粉和纳米改性复合粉体，搅拌混匀后依次加入模板剂、氢氟酸制得分子筛合成凝胶，将分子筛合成凝胶经晶化处理后，回收晶化产物即得ZSM‑5/AlPO4‑34复合分子筛。以该分子筛作为MTO催化剂载体。本发明制备ZSM‑5/AlPO4‑34复合分子筛的方法简单，晶化时间较短，适于大规模生产应用，其经济效益显著。采用本发明方法制得的ZSM‑5/AlPO4‑34复合分子筛应用于MTO反应中能够显著提高反应的选择性和催化效率。
Description
技术领域
本发明涉及一种制备MTO催化剂载体的方法，属于化工合成技术领域。
背景技术
MTO(Methanol To Olefin)是指由甲醇制取低碳烯烃（乙烯和丙烯）的化工工艺技术，为烯烃生产寻找了一条新的原料路线。不用石油而以甲醇为原料生产烯烃，不仅可使烯烃价格摆脱石油产品的影响，还能减少我国对石油资源的过度依赖。
MTO技术的关键是高性能催化剂的研制，早期对于MTO催化剂的研究主要以ZSM-5等中孔分子筛为主，ZSM-5的中大孔结构使其具有低碳少、寿命长等优点，但是由于其酸性太强，同时又具有烯烃收率低副产物多等缺点。1984年，UCC公司发明了SAPO-34分子筛用于MTO反应，其较小的孔径和较大的比表面积加快了MTO反应速率并且提高了反应的选择性，但是具有积碳高、易失活和寿命短等缺点。
鉴于甲醇制烯烃反应中的应用，需要制备一种ZSM-5/磷酸铝复合分子筛，与ZSM-5相比，ZSM-5/磷酸铝复合分子筛表现出了良好的协同作用和优良的催化性能。
发明内容
为了解决上述技术问题，本发明的目的是提供一种制备MTO催化剂载体的方法，具体步骤如下：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）将铝源、磷源加入水中搅拌待溶解完全，再加入ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入模板剂、氢氟酸，待搅拌3～5小时后制得纳米改性分子筛合成凝胶；
（3）将步骤（2）的分子筛合成凝胶在150～190℃下晶化12～24小时后冷却至室温，过滤，洗涤、在60-80℃下干燥，再在350～580℃下焙烧4～8小时即得纳米改性复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
所述铝源、磷源、模板剂、氢氟酸和水的摩尔比为铝源:磷源:模板剂: 氢氟酸：水=1:（1.0～1.5）:（0.5～2）:（0.1～0.2）：（50～300）；
所述的模板剂为吗啉、哌啶或吡啶。
所述的铝源为拟薄水铝石、异丙醇铝、氢氧化铝、氧化铝中的一种或两种任意比例的混合物。
所述的磷源为正磷酸。
步骤（1）中的酸选自盐酸、硝酸、甲酸、乙酸中的一种或几种。
步骤（3）中合成凝胶在160～180℃水热晶化18小时，干燥温度为60～80℃。
所述ZSM-5原粉的质量占分子筛合成凝胶总量的约1/10～1/5。
本发明的有益效果：
本发明制备纳米改性ZSM-5/AlPO4-34复合分子筛的方法简单，晶化时间较短，适于大规模生产应用，其经济效益显著。分子筛中还采用了特定配比的改性纳米复合粉体，经过表面改性的上述纳米复合粉体可有效改善分子筛的附着性、强度、韧性和耐高温性。ZSM-5/AlPO4-34复合分子筛特定组成中各组分的相互协同，在应用于MTO反应中能够显著提高反应的选择性和催化效率。
具体实施方式
实施例1
本实施例中纳米改性ZSM-5/AlPO4-34复合分子筛的制备方法具体包括以下步骤：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）按照摩尔比为（异丙醇铝+氧化铝）:正磷酸:（哌啶+吡啶）:氢氟酸：去离子水=1:1.0:0.5:0.1：50取各组分，将异丙醇铝和氧化铝石分别添加入到去离子水中搅拌6小时，待溶解完全后加入正磷酸搅拌3小时，再加入硅铝比为50的ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入哌啶和吡啶，以及氢氟酸，ZSM-5原粉的质量占分子筛合成凝胶总量的1/5，待搅拌3小时制得分子筛合成凝胶；
（3）将步骤（2）中分子筛合成凝胶移至带聚四氟乙烯内衬的不锈钢晶化釜中，在150℃下晶化24小时后冷却至室温，抽滤，洗涤至中性后在80℃下干燥6小时，再在580℃下焙烧4小时即得ZSM-5/AlPO4-34复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
实施例2
本实施例中纳米改性ZSM-5/AlPO4-34复合分子筛的制备方法具体包括以下步骤：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）按照摩尔比为（氢氧化铝+拟薄水铝石）:正磷酸:（吗啉+吡啶）:氢氟酸：去离子水=1: 1.2: 1: 0.15：200取各组分，将氢氧化铝和拟薄水铝石分别添加入到去离子水中搅拌8小时，待溶解完全后加入正磷酸搅拌3小时，再加入硅铝比为50的ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入吗啉和吡啶，以及氢氟酸，ZSM-5原粉的质量占分子筛合成凝胶总量的1/7，待搅拌4小时制得分子筛合成凝胶；
（3）将步骤（2）中分子筛合成凝胶移至带聚四氟乙烯内衬的不锈钢晶化釜中，在在180℃下晶化18小时，然后冷却至室温，抽滤，洗涤至中性后在70℃下干燥8小时，再在450℃下焙烧6小时即得ZSM-5/AlPO4-34复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
实施例3
本实施例中纳米改性ZSM-5/AlPO4-34复合分子筛的制备方法具体包括以下步骤：
（1）取粒径均为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）按照摩尔比为（异丙醇铝+拟薄水铝石）:正磷酸:（哌啶+吡啶）:氢氟酸：去离子水=1: 1.5: 2: 0.2：300取各组分，将异丙醇铝和拟薄水铝石分别添加入到去离子水中搅拌8小时，待溶解完全后加入正磷酸搅拌3小时，再加入硅铝比为50的ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入哌啶和吡啶，以及氢氟酸，ZSM-5原粉的质量占分子筛合成凝胶总量的1/5，待搅拌5小时制得分子筛合成凝胶；
（3）将步骤（2）中分子筛合成凝胶移至带聚四氟乙烯内衬的不锈钢晶化釜中，在在190℃下晶化12小时，然后冷却至室温，抽滤，洗涤至中性后在60℃下干燥10小时，再在350℃下焙烧8小时即得ZSM-5/AlPO4-34复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂。
Claims (3)
1.一种MTO催化剂载体的制备方法，其特征在于：具体步骤如下：
（1）取粒径均约为40-50nm的二氧化硅、二氧化钛和氧化银的混合粉体加入容器中，其中二氧化硅、二氧化钛和氧化银的质量比为2.8：2：1.6，而后加入聚乙烯醇和水的混合溶液，室温下搅拌分散60分钟，而后加入硅烷偶联剂KH550和酸，其中硅烷偶联剂KH550与酸的摩尔比为1:1，70℃搅拌反应5h，而后降温至室温，过滤，得到纳米改性复合粉体；
（2）将铝源、磷源加入水中搅拌待溶解完全，再加入ZSM-5原粉和步骤（1）得到的纳米改性复合粉体继续搅拌，并加入模板剂、氢氟酸，待搅拌3～5小时后制得纳米改性分子筛合成凝胶；
（3）将步骤（2）的分子筛合成凝胶在约160～180℃下晶化18小时后冷却至室温，过滤，洗涤、在70℃下干燥，再在350～580℃下焙烧4～8小时即得纳米改性复合分子筛；
（4）将步骤（3）中制得的纳米改性复合分子筛做为载体用于MTO催化剂；
所述铝源、磷源、模板剂、氢氟酸和水的摩尔比为铝源:磷源:模板剂: 氢氟酸：水=1:（1.0～1.5）:（0.5～2）:（0.1～0.2）：（50～300）；
所述的模板剂为吗啉、哌啶或吡啶；
所述的铝源为拟薄水铝石、异丙醇铝、氢氧化铝、氧化铝中的一种或两种任意比例的混合物；
所述ZSM-5原粉的质量占分子筛合成凝胶总量的1/10～1/5。
2.根据权利要求1所述的方法，其特征在于：所述的磷源为正磷酸。
3.根据权利要求1所述的方法，其特征在于：步骤（1）中的酸选自盐酸、硝酸、甲酸、乙酸中的一种或几种。
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