合成二甲醚的固体酸催化剂研究
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摘要
二甲醚作为一种重要的化工原料和可以替代液化石油气和柴油的清洁燃料,实现其经济的合成,对我国能源的多样化、清洁化具有重要的现实意义。
二甲醚可采用一氧化碳和氢气(合成气)为原料,先通过合成甲醇再由甲醇脱水来合成,或由合成气直接来合成。这两种二甲醚合成的工艺技术均需固体酸作为甲醇脱水的催化剂,目前最常用的甲醇脱水的固体酸催化剂是y-Al2O3和酸性分子筛。单纯的y-Al2O3催化剂酸性弱,虽然反应过程中稳定性高,但在反应温度300℃以上时才有足够的合成二甲醚活性,在热力学上不利于甲醇的转化,且反应的负荷低。分子筛催化剂酸性强、酸量高,较低温度时就有很高的甲醇转化率,但甲醇脱水的副产物多,催化剂表面易积碳,失活现象明显。因此,调整固体酸催化剂的酸量及其酸性强度,探索固体酸催化剂的合成或改性方法,不论对甲醇气相合成法还是合成气一步法合成二甲醚都有着十分重要的意义。
本论文以HZSM-5分子筛作为甲醇脱水的固体酸催化剂,通过高温水蒸气处理、含氟溶液改性及合成具有多级孔性质的HZSM-5分子筛的途径考察催化剂组成、酸性、孔结构、比表面积等性质对合成二甲醚反应的影响,获得了以下的的主要研究结果：
研究了高温水蒸汽处理对HZSM-5分子筛的酸性、孔道、硅铝比的修饰及其在甲醇脱水反应和合成气一步法合成二甲醚反应中催化性能的改进效果。结果发现：500℃水蒸汽处理2h的样品,在甲醇脱水反应中稳定性很好；但是600℃水蒸汽处理2h的样品,生成的非骨架铝会堵塞分子筛的孔道使催化剂的比表面积和孔体积都减少,甲醇脱水的反应活性低,且生成的非骨架铝在合成气直接合成二甲醚的反应中会促进副反应的发生。
鉴于水蒸气处理时分子筛催化剂表面总酸量减小,酸量低不利于甲醇脱水反应的进行,从而进一步采用了含氟溶液处理了HZSM-5分子筛,并考察其作为甲醇脱水反应的催化剂的催化性能。由于F的电子效应,低浓度氟化氨处理时虽然催化剂表面总酸量变化不大但是酸中心的强度增强,因此甲醇脱水活性明显提高。而氟化铝溶液处理的HZSM-5分子筛上,虽然溶液中F-仍然存在,但是由于A13+的存在,导致作用机理不同,在甲醇脱水反应中活性也有明显提高,但是催化剂的稳定性比单独氟化铵处理时要好。
由于含氟溶液改性的分子筛表现出优异的甲醇脱水催化性能,而含氟溶液对环境污染严重,于是本论文尝试采用氟化铝粉末跟HZSM-5分子筛固相机械混合的方式对分子筛进行了改性,且通过调变AlF3·3H2O的加入量就可以达到明显改变分子筛酸性及织构的效果,并将改性后的分子筛用于甲醇脱水和合成气直接合成二甲醚反应中,研究其催化性能。研究表明：在AlF3改性HZSM-5分子筛过程中,A1F3的量小于2wt%时,分子筛的补铝作用占主导地位；当A1F3的量增大至3wt%时脱铝作用占主导地位。2wt%AlF3改性的分子筛上催化剂上甲醇脱水的活性和稳定性都比较好。在合成气直接合成二甲醚反应中Cu-Zn/HZ(2)催化剂上也显出高的一氧化碳转化率,但是由于酸性相对较强,甲醇的选择性降低的同时,副产物也相应增多。
为了探明介孔在合成二甲醚反应中所起的作用,本文将合成的多级孔ZSM-5分子筛用于合成二甲醚的反应中。在甲醇脱水反应中具有多级介孔的HZSM-5分子筛表现出比常规微孔HZSM-5分子筛更高的反应稳定性和对二甲醚选择性。实验结果还表明微孔分子筛上更加有利于甲醇的吸附,而在甲醇吸附强的样品上,容易产生副产物。虽然合成的多级孔ZSM-5分子筛表面酸性差异较大,但是在合成气直接合成二甲醚反应中,却表现出基本相似的一氧化碳转化率。
通过对改性以及合成的HZSM-5分子筛作为固体酸催化剂在甲醇脱水和合成气一步法合成二甲醚反应中活性差异的比较,对固体酸催化剂的织构、酸性和形貌特征对合成二甲醚的影响做出总结。结果表明：多级孔分子筛作为载体组成双功能催化剂时,虽然酸性差异很大,但是所有样品的一氧化碳的转化率和二甲醚的选择性都很接近。而水蒸气脱铝和固体氟化铝脱铝制备的HZSM-5载体中,酸性较小时,一氧化碳的转化率都比较低,甲醇的选择性和烯烃的选择性都比较高,说明了在合成气直接合成二甲醚中,对载体酸性的要求不大,载体织构在反应中起到更为重要的作用。
With the rapid growth of the national economy, the demand of energy becomes a widely existed problem both in china and all over the world. Dimethyl ether (DME) is an important chemical material and also a potential clean energy which can substitute diesel and liquefied petroleum gas. Synthesis of DME plays an important role in the aspect of rational use of energy in china.
At Present, DME mainly produced from syngas by the following two traditional processes: frist synthesis methanol and then dehydration to DME (so called MTD) over the solid-acid catalyst, the second way is direct synthesis of DME form syngas (so called STD) over the bifunctional catalysts consisting of methanol synthesis component and solid-acid component. For MTD process, a suitable solid catalyst is the key factor for its excellent performance.For STD process, the methanol synthesis component has been used successfully for several decades and the reaction mechanism of the catalysts has been well studied. In contrast to methanol synthesis, the methanol dehydration component has received less attention. Among these solid-acid catalysts, γ-Al2O3and HZSM-5are the most widely materials, however, the most suitable temperature for γ-Al2O3is above300℃, and undesirable byproducts in DME synthesis such as hydrocarbons and even coke formed on the HZSM-5zeolite catalyst due to the presence of strong acid sites. So it become very important to search new solid-acid catalyst and develop the post treatment techniques for the MTD and STD process.
On the basis of the previous study, in this work we choose HZSM-5as research objectives and study its acidity and texture properties, and got the following conclusions:
Study thermal steam modified HZSM-5zeolite and apply them in the MTD and STD processes. The surface acidity, pores structures, and Si/Al ratio has changed in the dealumination process. The result shows that HZSM-5treat at500℃for2h shows better stability than parent zeolite in MTD process, but for sample which treat at600℃for2h, amorphous fragments produced in the dealumination process blocked some micropores.Amorphous alumiums deduce the side reaction in the STD process.
Thermal steam method made the total acity on the surface of HZSM-5decreased, which result in a decreased activity of methanol dehydration. So this paper tried to study fluoride solution modified HZSM-5zeolite and apply them in the MTD and STD processes. The incorporation of F-species as electron withdrawing compounds reduce the amount of acid sites but enhance the surface acid strength. NH4F modified HZSM-5zeolite shows excellent activity in MTD process, but in STD process it increase the selectivities for undesired by-products like hydrocarbons and CO2due to the new formed strong acid site
Fluoride solution modified HZSM-5zeolite exhibed excellent methanol dehydration activities, but fluoride solution seriously pollute the environmental, so modify HZSM-5zeolite with solid AlF3·3H2O by the way of mechanical mixture route was tried and apply them in the MTD and STD processes. The structure, texture, and acidity of HZSM-5catalysts can be adjusted with loading of AIF3. The results show that2wt%of AIF3modification could increase the framework aluminum content and the surface area of HZSM-5, however, when the loading of AIF3came to3wt%or more, the contrary results were obtained, which could be ascribed to the dealumination of the zeolitic framework。2wt%AlF3-modified HZSM-5exhibited much higher activity and better stability than parent HZSM-5in MTD process. In the STD process, it shows relative high selectivities for undesired by-products due to the strong acid site.
In order to ascertain the role of mesopores in the synthesis of dimethyl ether reaction. The application of HZSM-5with hierarchical mesopores to synthesis DME process was performed in this work. The hierarchical mesopore ZSM-5zeolites shows better stability and high DME selectivity than conventional micropore HZSM-5zeolites for MTD process. The results also show that micropore was more favorable for methanol adsorption, however, the stronger methanol adsorption on the zeolite, the easier by-products can be produced. The acidity properties on the hierarchical mesopore HZSM-5are quite different, whereas the conversion of carbon monoxide was scarcely affected.
Through comparison of the MTD and STD activities on the various method modified HZSM-5zeolite, we conclude the role of texture, acidity and morphology of HZSM-5catalysts played in the synthesis of DME process. In the STD process, the acidity properties on the hierarchical mesopore HZSM-5are quite different, whereas the conversion of carbon monoxide and selectivity of DME were scarcely affected.However, on the thermal steam and AlF3modified HZSM-5, when dealumination cause acidity decrease obviously, the conversion of carbon monoxide was decrease correspondingly and selectivities for methanol and by-products were increased obviously. This indicate the texture property of solid-acid was more important than acidity property in the STD process.
二甲醚可采用一氧化碳和氢气(合成气)为原料,先通过合成甲醇再由甲醇脱水来合成,或由合成气直接来合成。这两种二甲醚合成的工艺技术均需固体酸作为甲醇脱水的催化剂,目前最常用的甲醇脱水的固体酸催化剂是y-Al2O3和酸性分子筛。单纯的y-Al2O3催化剂酸性弱,虽然反应过程中稳定性高,但在反应温度300℃以上时才有足够的合成二甲醚活性,在热力学上不利于甲醇的转化,且反应的负荷低。分子筛催化剂酸性强、酸量高,较低温度时就有很高的甲醇转化率,但甲醇脱水的副产物多,催化剂表面易积碳,失活现象明显。因此,调整固体酸催化剂的酸量及其酸性强度,探索固体酸催化剂的合成或改性方法,不论对甲醇气相合成法还是合成气一步法合成二甲醚都有着十分重要的意义。
本论文以HZSM-5分子筛作为甲醇脱水的固体酸催化剂,通过高温水蒸气处理、含氟溶液改性及合成具有多级孔性质的HZSM-5分子筛的途径考察催化剂组成、酸性、孔结构、比表面积等性质对合成二甲醚反应的影响,获得了以下的的主要研究结果：
研究了高温水蒸汽处理对HZSM-5分子筛的酸性、孔道、硅铝比的修饰及其在甲醇脱水反应和合成气一步法合成二甲醚反应中催化性能的改进效果。结果发现：500℃水蒸汽处理2h的样品,在甲醇脱水反应中稳定性很好；但是600℃水蒸汽处理2h的样品,生成的非骨架铝会堵塞分子筛的孔道使催化剂的比表面积和孔体积都减少,甲醇脱水的反应活性低,且生成的非骨架铝在合成气直接合成二甲醚的反应中会促进副反应的发生。
鉴于水蒸气处理时分子筛催化剂表面总酸量减小,酸量低不利于甲醇脱水反应的进行,从而进一步采用了含氟溶液处理了HZSM-5分子筛,并考察其作为甲醇脱水反应的催化剂的催化性能。由于F的电子效应,低浓度氟化氨处理时虽然催化剂表面总酸量变化不大但是酸中心的强度增强,因此甲醇脱水活性明显提高。而氟化铝溶液处理的HZSM-5分子筛上,虽然溶液中F-仍然存在,但是由于A13+的存在,导致作用机理不同,在甲醇脱水反应中活性也有明显提高,但是催化剂的稳定性比单独氟化铵处理时要好。
由于含氟溶液改性的分子筛表现出优异的甲醇脱水催化性能,而含氟溶液对环境污染严重,于是本论文尝试采用氟化铝粉末跟HZSM-5分子筛固相机械混合的方式对分子筛进行了改性,且通过调变AlF3·3H2O的加入量就可以达到明显改变分子筛酸性及织构的效果,并将改性后的分子筛用于甲醇脱水和合成气直接合成二甲醚反应中,研究其催化性能。研究表明：在AlF3改性HZSM-5分子筛过程中,A1F3的量小于2wt%时,分子筛的补铝作用占主导地位；当A1F3的量增大至3wt%时脱铝作用占主导地位。2wt%AlF3改性的分子筛上催化剂上甲醇脱水的活性和稳定性都比较好。在合成气直接合成二甲醚反应中Cu-Zn/HZ(2)催化剂上也显出高的一氧化碳转化率,但是由于酸性相对较强,甲醇的选择性降低的同时,副产物也相应增多。
为了探明介孔在合成二甲醚反应中所起的作用,本文将合成的多级孔ZSM-5分子筛用于合成二甲醚的反应中。在甲醇脱水反应中具有多级介孔的HZSM-5分子筛表现出比常规微孔HZSM-5分子筛更高的反应稳定性和对二甲醚选择性。实验结果还表明微孔分子筛上更加有利于甲醇的吸附,而在甲醇吸附强的样品上,容易产生副产物。虽然合成的多级孔ZSM-5分子筛表面酸性差异较大,但是在合成气直接合成二甲醚反应中,却表现出基本相似的一氧化碳转化率。
通过对改性以及合成的HZSM-5分子筛作为固体酸催化剂在甲醇脱水和合成气一步法合成二甲醚反应中活性差异的比较,对固体酸催化剂的织构、酸性和形貌特征对合成二甲醚的影响做出总结。结果表明：多级孔分子筛作为载体组成双功能催化剂时,虽然酸性差异很大,但是所有样品的一氧化碳的转化率和二甲醚的选择性都很接近。而水蒸气脱铝和固体氟化铝脱铝制备的HZSM-5载体中,酸性较小时,一氧化碳的转化率都比较低,甲醇的选择性和烯烃的选择性都比较高,说明了在合成气直接合成二甲醚中,对载体酸性的要求不大,载体织构在反应中起到更为重要的作用。
With the rapid growth of the national economy, the demand of energy becomes a widely existed problem both in china and all over the world. Dimethyl ether (DME) is an important chemical material and also a potential clean energy which can substitute diesel and liquefied petroleum gas. Synthesis of DME plays an important role in the aspect of rational use of energy in china.
At Present, DME mainly produced from syngas by the following two traditional processes: frist synthesis methanol and then dehydration to DME (so called MTD) over the solid-acid catalyst, the second way is direct synthesis of DME form syngas (so called STD) over the bifunctional catalysts consisting of methanol synthesis component and solid-acid component. For MTD process, a suitable solid catalyst is the key factor for its excellent performance.For STD process, the methanol synthesis component has been used successfully for several decades and the reaction mechanism of the catalysts has been well studied. In contrast to methanol synthesis, the methanol dehydration component has received less attention. Among these solid-acid catalysts, γ-Al2O3and HZSM-5are the most widely materials, however, the most suitable temperature for γ-Al2O3is above300℃, and undesirable byproducts in DME synthesis such as hydrocarbons and even coke formed on the HZSM-5zeolite catalyst due to the presence of strong acid sites. So it become very important to search new solid-acid catalyst and develop the post treatment techniques for the MTD and STD process.
On the basis of the previous study, in this work we choose HZSM-5as research objectives and study its acidity and texture properties, and got the following conclusions:
Study thermal steam modified HZSM-5zeolite and apply them in the MTD and STD processes. The surface acidity, pores structures, and Si/Al ratio has changed in the dealumination process. The result shows that HZSM-5treat at500℃for2h shows better stability than parent zeolite in MTD process, but for sample which treat at600℃for2h, amorphous fragments produced in the dealumination process blocked some micropores.Amorphous alumiums deduce the side reaction in the STD process.
Thermal steam method made the total acity on the surface of HZSM-5decreased, which result in a decreased activity of methanol dehydration. So this paper tried to study fluoride solution modified HZSM-5zeolite and apply them in the MTD and STD processes. The incorporation of F-species as electron withdrawing compounds reduce the amount of acid sites but enhance the surface acid strength. NH4F modified HZSM-5zeolite shows excellent activity in MTD process, but in STD process it increase the selectivities for undesired by-products like hydrocarbons and CO2due to the new formed strong acid site
Fluoride solution modified HZSM-5zeolite exhibed excellent methanol dehydration activities, but fluoride solution seriously pollute the environmental, so modify HZSM-5zeolite with solid AlF3·3H2O by the way of mechanical mixture route was tried and apply them in the MTD and STD processes. The structure, texture, and acidity of HZSM-5catalysts can be adjusted with loading of AIF3. The results show that2wt%of AIF3modification could increase the framework aluminum content and the surface area of HZSM-5, however, when the loading of AIF3came to3wt%or more, the contrary results were obtained, which could be ascribed to the dealumination of the zeolitic framework。2wt%AlF3-modified HZSM-5exhibited much higher activity and better stability than parent HZSM-5in MTD process. In the STD process, it shows relative high selectivities for undesired by-products due to the strong acid site.
In order to ascertain the role of mesopores in the synthesis of dimethyl ether reaction. The application of HZSM-5with hierarchical mesopores to synthesis DME process was performed in this work. The hierarchical mesopore ZSM-5zeolites shows better stability and high DME selectivity than conventional micropore HZSM-5zeolites for MTD process. The results also show that micropore was more favorable for methanol adsorption, however, the stronger methanol adsorption on the zeolite, the easier by-products can be produced. The acidity properties on the hierarchical mesopore HZSM-5are quite different, whereas the conversion of carbon monoxide was scarcely affected.
Through comparison of the MTD and STD activities on the various method modified HZSM-5zeolite, we conclude the role of texture, acidity and morphology of HZSM-5catalysts played in the synthesis of DME process. In the STD process, the acidity properties on the hierarchical mesopore HZSM-5are quite different, whereas the conversion of carbon monoxide and selectivity of DME were scarcely affected.However, on the thermal steam and AlF3modified HZSM-5, when dealumination cause acidity decrease obviously, the conversion of carbon monoxide was decrease correspondingly and selectivities for methanol and by-products were increased obviously. This indicate the texture property of solid-acid was more important than acidity property in the STD process.
引文
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