CN108273548A - 一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法 - Google Patents
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种ZnO‑Al2O3@SAPO‑34核壳结构催化剂的制备方法，包括：粉末ZnO‑Al2O3的制备：按原料摩尔配比Al2O3:P2O5:SiO2:MOR:H2O=1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO‑Al2O3:SAPO‑34为1:4‑4:1将ZnO‑Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，190‑210℃水热晶化24‑48h、冷却、过滤、去离子水洗涤至中性、105℃烘干6h、于500‑600℃下焙烧3h，制得。本发明制得的催化剂在CO2加氢经甲醇制低碳烯烃两步法工艺中能同时提高二氧化碳转化率和低碳烯烃选择性。
Description
技术领域
本发明属化工技术领域，具体涉及一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法。
背景技术
锌铝 (ZnO-Al2O3) 二组分催化剂是CO2催化加氢合成甲醇工艺抗烧结稳定性和抗硫能力较强、且效果较好的一类金属氧化物催化剂。SAPO-34是由SiO4、AlO4和PO4三种四面体单元交错排列成三维交叉孔道结构的微孔磷酸硅铝系分子筛，因其具有丰富可调B酸性质、较高比表面积及独特微孔产物择形功能等特点，被广泛用于甲醇催化裂化制低碳烯烃工艺（MTO）。据此，将金属氧化物和酸性分子筛进行耦合制备双功能核壳催化剂，并应用到CO2加氢经甲醇制低碳烯烃工艺中，为CO2加氢制低碳烯烃工艺新型结构催化剂设计开发开辟了一条新的路径。而现有复合催化剂活性组分为随机分布，且结构仅提供开放式反应环境，更为重要的是，以传统纳米铜粒子为活性组分的分布结构抗烧结稳定性极差，不能有效解决CO2加氢经甲醇制低碳烯烃两步法工艺中CO2加氢合成甲醇工艺和甲醇催化转化制低碳烯烃工艺要求不同反应生成和解离转化环境条件的矛盾问题，致使现有复合催化剂催化效果仍不佳。
发明内容
本发明的目的在于提供一种在CO2加氢经甲醇制低碳烯烃两步法工艺中能同时提高二氧化碳转化率和低碳烯烃选择性的ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法。
本发明的目的是通过下述技术方案实现的。
本发明的一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h，磨细制得200-400目的ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2:MOR:H2O=1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为1:4-4:1将ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，190-210 ℃水热晶化24-48h、冷却、过滤、去离子水洗涤至中性、105℃烘干6h、于500-600℃下焙烧3h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
本发明与现有技术相比，具有明显的有益效果，从以上技术方案可知：制备一种以介孔ZnO-Al2O3为核相，微孔SAPO-34为壳相的新型核壳结构催化剂，核相ZnO-Al2O3的构造促进锌铝形成固溶结构，进而产生更多氧空位及特殊表面L酸碱性，提高CO2转化率；核相Al2O3与壳相SAPO-34形成适宜L-B酸协同催化中心，增强甲醇较低温度下的解离吸附，提高较低温度下甲醇转化率；构造以SAPO-34为壳相的特殊反应路径增强低碳烯烃选择性，抑制副产物生成；微-介孔体系的层级结构构造减弱分子的扩散限制，缓解积碳形成，延长催化剂寿命。即以本发明制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在CO2加氢制低碳烯烃工艺，在较低温度下不仅具有较高反应活性，还具有较高低碳烯烃选择性，同时还能延长催化剂反应寿命。
下面通过具体实施例对本发明作进一步说明。
具体实施方式
实施例1
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h制得ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2: MOR: H2O =1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为1:4将200目ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，190 ℃水热晶化24 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于500 ℃下焙烧3 h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
使用例：制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中（反应压力：3.0 MPa，反应温度：325 ℃，重时空速：3500 h-1，氮气流速：30 mL·min-1，H2/CO2摩尔比3.0:1.0），测得CO2转化率58.41%，低碳烯烃选择性69.93%。
实施例2
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h制得ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2: MOR: H2O =1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为4:1将300目ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，200 ℃水热晶化36 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于550 ℃下焙烧3 h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
使用例：制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中（反应压力：3.0 MPa，反应温度：325 ℃，重时空速：3500 h-1，氮气流速：30 mL·min-1，H2/CO2摩尔比3.0:1.0），测得CO2转化率63.22%，低碳烯烃选择性81.48%。
实施例3
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h制得ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2: MOR: H2O =1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为1:2将400目ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，210 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于600 ℃下焙烧3 h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
使用例：制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中（反应压力：3.0 MPa，反应温度：325 ℃，重时空速：3500 h-1，氮气流速：30 mL·min-1，H2/CO2摩尔比3.0:1.0），测得CO2转化率61.33%，低碳烯烃选择性80.42%。
实施例4
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h制得ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2: MOR: H2O =1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为2:1将200目ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，200 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于550 ℃下焙烧3 h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
使用例：制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中（反应压力：3.0 MPa，反应温度：325 ℃，重时空速：3500 h-1，氮气流速：30 mL·min-1，H2/CO2摩尔比3.0:1.0），测得CO2转化率57.44%，低碳烯烃选择性79.14%。
实施例5
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h制得ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2: MOR: H2O =1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为1:3将200目ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，200 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于550 ℃下焙烧3 h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
使用例：制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中（反应压力：3.0 MPa，反应温度：325 ℃，重时空速：3500 h-1，氮气流速：30 mL·min-1，H2/CO2摩尔比3.0:1.0），测得CO2转化率58.17%，低碳烯烃选择性64.51%。
实施例6
一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h制得ZnO-Al2O3粉末。
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5:SiO2: MOR: H2O =1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为3:1将200目ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，200 ℃水热晶化48 h、冷却、过滤、去离子水洗涤至中性、105 ℃烘干6 h、于550 ℃下焙烧3 h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
使用例：制得ZnO-Al2O3@SAPO-34核壳结构催化剂应用在二氧化碳加氢合成低碳烯烃工艺中（反应压力：3.0 MPa，反应温度：325℃，重时空速：3500 h-1，氮气流速：30 mL·min-1，H2/CO2摩尔比3.0:1.0），测得CO2转化率57.69%，低碳烯烃选择性63.20%。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，任何未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
Claims (2)
1.一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，包括以下步骤：
（1）ZnO-Al2O3的制备：按原料摩尔配比NH4CO3:Al(NO3)3·9H2O: Zn(NO3)2·6H2O=1.7:1.0:0.2，搅拌下，将1.0 mol·L-1碳酸铵溶液以3ml/min的流速加至锌铝混合溶液中，70℃下持续搅拌老化2h，过滤、洗涤、110℃烘干4h，400℃焙烧4h，磨细制得200-400目的ZnO-Al2O3粉末；
（2）ZnO-Al2O3@SAPO-34核壳结构催化剂的制备：按原料摩尔配比Al2O3: P2O5: SiO2:MOR:H2O=1.0:0.8:0.6:2.5:80，搅拌下，依次将拟薄水铝石，正硅酸乙酯和模板剂吗啡啉加入到正磷酸溶液中，持续搅拌均匀，室温下搅拌老化24h形成溶胶体系，按核壳质量比ZnO-Al2O3:SAPO-34为1:4-4:1将ZnO-Al2O3粉末投入至该体系中，继续搅拌均匀后转入反应釜中，190-210 ℃水热晶化24-48h、冷却、过滤、去离子水洗涤至中性、105℃烘干6h、于500-600℃下焙烧3h，制得ZnO-Al2O3@SAPO-34核壳结构催化剂。
2.如权利要求1所述的一种ZnO-Al2O3@SAPO-34核壳结构催化剂的制备方法，其中：ZnO-Al2O3粉末目数为200-400目。
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| CN114768862A (zh) * | 2022-05-25 | 2022-07-22 | 山东科技大学 | 核壳型Co@Six/SAPO-34双功能催化剂及其制备方法和应用 |
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| CN114768862A (zh) * | 2022-05-25 | 2022-07-22 | 山东科技大学 | 核壳型Co@Six/SAPO-34双功能催化剂及其制备方法和应用 |
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