CN113184860A - 一种孔结构可控的硅铝胶制备方法 - Google Patents
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011148 porous material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 8
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- 238000003756 stirring Methods 0.000 claims description 38
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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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 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 239000002808 molecular sieve Substances 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 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 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
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- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/16—Preparation of silica xerogels
- C01B33/163—Preparation of silica xerogels by hydrolysis of organosilicon compounds, e.g. ethyl orthosilicate
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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Abstract
本发明涉及一种孔结构可控的硅铝胶制备方法，属于催化剂领域，具体是通过在凝胶成形过程中，调控溶液pH值，使其保持在一定范围内，由此在不同酸碱度下形成的硅铝胶，其孔结构大小也不同，从而达到孔结构可控的目的。所述孔结构可控的硅铝胶不仅可以直接作为催化剂，而且根据其孔结构可控的特点也可作为优良的催化剂载体。本发明目的在于解决现有催化剂活性低、重复性差、活性组分流失的问题，用于制备出高稳定性、高活性、易于回收、环境友好的催化剂。
Description
技术领域
本发明涉及一种孔结构可控的硅铝胶制备方法，属于催化剂领域，具体是通过在凝胶成形过程中，调控溶液pH值，使其保持在一定范围内，由此在不同酸碱度下形成的硅铝胶，其孔结构大小也不同，从而达到孔结构可控的目的。
背景技术
硅铝胶由于它具有大孔结构，这有利于物质在孔道内的加速扩散，介孔的存在可以实现酸性活位点的浓度的控制。无定形的硅铝酸氧化物在实际应用中占据着非常重要的位置。硅铝酸氧化物常用于狄尔斯反应、重油的加氢处理、异丙基苯断裂、噻吩和苯并噻吩的加氢脱硫、1-丁烯的复分解反应。除此以外，还可用于中密度聚乙烯的催化降解。据相关报道，现阶段具有微孔与介孔结构的硅铝酸氧化物可以促进碳氢化合物的形成，很大程度上影响汽油的辛烷值。所以制备一种孔结构可控的硅铝胶，以期能够适应大规模工业化生产的要求越来越成为研究的重点。
目前存在的硅铝胶制备方案多为在硅源和铝源选用上有所区别，即用不同的原料制备硅铝胶。例如专利CN110252385A公开了一种以废催化剂为原料制备的硅粉，与粘结剂、分子筛制备催化裂化催化剂的方法。该催化裂化催化剂采用硅粉作为载体，有更高的重油裂解能力，转化率提高，总液收提高，轻质油收率提高，降低干气、液化气产率，焦炭选择性更好；专利CN112371165A公开了一种以NaY母液为原料制备的硅铝胶，其针对结晶度高和低的NaY的母液均可用于硅铝胶的合成。用其制得的硅铝胶与高岭土、粘结剂打浆，进一步加入Y型分子筛，成胶、造粒、洗涤、干燥，得到催化剂成品；专利CN106902799A公开了一种以泡花碱、硫酸、拟薄水铝石为主要生产原料，其中泡花碱和硫酸成胶后需经老化扩孔和酸泡水洗，合成一种用于合成三聚氰胺高铝催化剂。
本发明中的硅铝胶，其硅源为金属醇盐，铝源为硝酸铝，通过对制备过程中酸碱度的调节，使得硅铝成分在不同PH环境中水解、凝结，从而实现对硅铝胶孔结构的控制。经过成胶、干燥、煅烧等一系列步骤，最终得到催化剂成品。
发明内容
本发明的目的是提供一种孔结构可控的硅铝胶制备方法。采用此方法生产的硅铝胶具有孔结构可控、稳定性高、高活性、易于回收、环境友好等优点。
为达到上述目的，本发明采用如下技术方案：
1.基于一种孔结构可控的硅铝胶制备方法，其特征在于，包括以下步骤：
（1）凝胶的形成
称取一定质量的正硅酸乙酯于无水乙醇中，缓慢搅拌均匀；称取一定质量的硝酸铝于蒸馏水中，缓慢搅拌至溶解；将所得正硅酸乙酯溶液加入到硝酸铝溶液中，缓慢搅拌均匀；向形成的混合溶液中滴加一定浓度的液体酸、碱，调节pH值为4-11，于20-60℃下搅拌1-4h，形成凝胶；上述正硅酸乙酯与无水乙醇的摩尔比为1:5-12，硝酸铝与蒸馏水的摩尔比为1:0-5；
（2）共沸带水
将步骤（1）中形成的凝胶与一定质量的带水剂混合，剧烈搅拌形成悬浮液；将所得悬浮液在90-100℃下蒸馏0.5-3h；提升温度至100-120℃下蒸馏0.5-1h；
（3）硅铝胶的形成
将步骤（2）中所得凝胶于100-120℃下干燥10-12h，600-900℃下煅烧1-4h得到硅铝胶；
2.所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（1）中液体酸、碱包括但并不限于冰醋酸，氨水；
3.所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（1）中滴加氨水的质量分数为25%，冰醋酸的质量分数为100%；
4.所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（1）中调节pH值为4-11；
5.所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（2）中带水剂包括但并不限于正丁醇，正丙醇，异丁醇，异丙醇，优选正丁醇；
6.所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（2）中加入带水剂的质量与加入氨水的质量比为1.2-1.5:1，优选1.2-1.3:1；如果脱离此范围，将会导致带水剂的作用下降，带水效果降低。
具体实施方式
实施例1
取20g正硅酸乙酯和50g无水乙醇配置成溶液，搅拌均匀待用；取35g硝酸铝和12g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，50℃下加入氨水，调节溶液pH值为7，搅拌2h；
将上一步中制得的凝胶与50g正丁醇剧烈搅拌混合，在93℃下蒸馏0.5h，之后在117℃下蒸馏0.5h；
将上一步中制得的去水凝胶在110℃条件下干燥10h，然后在800℃条件下煅烧2h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶孔径分布不均匀，微孔，中孔，大孔均有生成；
实施例2
取20g正硅酸乙酯和50g无水乙醇配置成溶液，搅拌均匀待用；取35g硝酸铝和12g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，50℃下加入氨水，调节溶液pH值为8，搅拌2h；
将上一步中制得的凝胶与70g正丁醇剧烈搅拌混合，在93℃下蒸馏0.5h，之后在117℃下蒸馏0.5h；
将上一步中制得的去水凝胶在110℃条件下干燥10h，然后在850℃条件下煅烧2h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶孔径分布较不均匀，微孔，中孔，大孔均有生成；但相比于实施例1，微孔形成减少；
实施例3
取20g正硅酸乙酯和45g无水乙醇配置成溶液，搅拌均匀待用；取35g硝酸铝和12g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，50℃下加入氨水，调节溶液pH值为9，搅拌2h；
将上一步中制得的凝胶与100g正丙醇剧烈搅拌混合，在95℃下蒸馏1h，之后在100℃下蒸馏0.5h；
将上一步中制得的去水凝胶在100℃条件下干燥12h，然后在800℃条件下煅烧2h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶不形成微孔，为大孔结构；
实施例4
取20g正硅酸乙酯和50g无水乙醇配置成溶液，搅拌均匀待用；取40g硝酸铝和12g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，40℃下加入氨水，调节溶液pH值为10，搅拌2h；
将上一步中制得的凝胶与140g正丙醇剧烈搅拌混合，在90℃下蒸馏1.5h，之后在100℃下蒸馏0.5h；
将上一步中制得的去水凝胶在100℃条件下干燥12h，然后在700℃条件下煅烧3h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶不形成微孔，为大孔结构；孔容相比于实施例3有所降低；
实施例5
取20g正硅酸乙酯和45g无水乙醇配置成溶液，搅拌均匀待用；取40g硝酸铝和15g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，40℃下加入氨水，调节溶液pH值为11，搅拌2h；
将上一步中制得的凝胶与200g异丁醇剧烈搅拌混合，在90℃下蒸馏2h，之后在110℃下蒸馏0.5h；
将上一步中制得的去水凝胶在120℃条件下干燥10h，然后在900℃条件下煅烧2h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶不形成微孔，为大孔结构；孔容相比于实施例3、4有所降低；
实施例6
取20g正硅酸乙酯和50g无水乙醇配置成溶液，搅拌均匀待用；取35g硝酸铝和12g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，50℃下加入冰醋酸，调节溶液pH为4，搅拌2h；
将上一步中制得的凝胶与50g正丁醇剧烈搅拌混合，在95℃下蒸馏0.5h，之后在117℃下蒸馏0.5h；
将上一步中制得的去水凝胶在110℃条件下干燥10h，然后在800℃条件下煅烧2h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶主要形成微孔；
实施例7
取20g正硅酸乙酯和50g无水乙醇配置成溶液，搅拌均匀待用；取35g硝酸铝和12g蒸馏水配置成溶液，溶解搅拌至均匀；将上述两种溶液混合均匀，50℃下加入冰醋酸，调节溶液pH值为5，搅拌2h；
将上一步中制得的凝胶与40g异丁醇剧烈搅拌混合，在93℃下蒸馏0.5h，之后在115℃下蒸馏0.5h；
将上一步中制得的去水凝胶在100℃条件下干燥12h，然后在750℃条件下煅烧3h，制得硅铝胶；
表征结果如表1所示，此条件下制备的硅铝胶主要形成微孔；但相比于实施例6，孔容有所增加；
各实施例催化剂性质
表1
综上所述，在不同的条件下可制备出不同孔容大小的硅铝胶，如表1所示；由此本发明制备出的硅铝胶，实现了对硅铝胶孔结构的控制；因为微孔和中孔的存在，可以使催化剂表现出大的表面积，大孔的存在有利于反应物和产物的输送，减少传输限制；根据这些特点，本发明可结合实际需要，制备出不同孔结构的硅铝胶。
Claims (6)
1.基于一种孔结构可控的硅铝胶制备方法，其特征在于，包括以下步骤：
（1）凝胶的形成
称取一定质量的正硅酸乙酯于无水乙醇中，缓慢搅拌均匀；称取一定质量的硝酸铝于蒸馏水中，缓慢搅拌至溶解；将所得正硅酸乙酯溶液加入到硝酸铝溶液中，缓慢搅拌均匀；向形成的混合溶液中滴加一定浓度的液体酸、碱，调节pH为4-11，于20-60℃下搅拌1-4h，形成凝胶；上述正硅酸乙酯与无水乙醇的摩尔比为1:5-12，硝酸铝与蒸馏水的摩尔比为1:0-5；
（2）共沸带水
将步骤（1）中形成的凝胶与一定质量的带水剂混合，剧烈搅拌形成悬浮液；将所得悬浮液在90-100℃下蒸馏0.5-3h；提升温度至100-120℃下蒸馏0.5-1h；
（3）硅铝胶的形成
将步骤（2）中所得凝胶于100-120℃下干燥10-12h，600-900℃下煅烧1-4h得到硅铝胶。
2.根据权利要求1所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（1）中液体酸、碱为冰醋酸，氨水。
3.根据权利要求1所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（1）中滴加氨水的质量分数为25%，冰醋酸的质量分数为100%。
4.根据权利要求1所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（1）中调节pH为4-11。
5.根据权利要求1所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（2）中带水剂为正丁醇，正丙醇，异丁醇，异丙醇。
6.根据权利要求1所述的孔结构可控的硅铝胶制备方法，其特征在于，步骤（2）中加入带水剂的质量与加入氨水的质量比为1.2-1.5:1。
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