合成气一步法合成二甲醚Cu-Zn-Mn/zeolite-Y催化剂及Mn作用的研究
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摘要
二甲醚作为一种重要的化工原料和理想的清洁替代能源,实现其经济地合成,对我国能源的多样化、清洁化具有重要的现实意义。合成气一步法合成二甲醚克服了甲醇合成反应的热力学限制,大大提高了CO的单程转化率。由于一步合成二甲醚过程中涉及甲醇合成、甲醇脱水和水汽变换三个反应之间相互耦合,因此要求其催化剂同时具有多种功能以及相互匹配。本论文以Y型分子筛负载Mn促进的铜基催化剂为基础,通过改变催化剂的组成、配比、制备方式和条件,系统地研究了该类催化剂的结构特点和反应特性,并对助剂Mn的作用及其产生作用的机制进行了探讨,获得的主要结果如下:
采用相同的共沉淀浸渍法制备了不同组成和组分配比的Cu-Mn/zeolite-Y、Cu-Zn/zeolite-Y和Cu-Zn-Mn/zeolite-Y系列催化剂,通过对其反应性能的考察,发现Cu-Mn/zeolite-Y催化剂虽然低温活性不够高,但其合成二甲醚反应的稳定性较好;调节Cu/Zn比可获得较高催化活性的Cu-Zn/zeolite-Y催化剂,但其稳定性不高;Cu-Zn-Mn/zeolite-Y催化剂与Cu-Zn/zeolite-Y催化剂相比,其催化活性和稳定性有很大的提高,CO转化率从58.5%增加到82.9%,并且对于Cu-Zn-Mn/zeolite-Y催化剂体系,Cu、Zn和Mn的含量在较宽的范围内,并不影响催化剂的合成二甲醚活性。
在Cu-Mn/zeolite-Y催化剂中,Cu与Mn之间可形成类尖晶石复合氧化物Cu_(1.5)Mn_(1.5)O_4,并且当催化剂的物相组成为CuO+Cu_(1.5)Mn_(1.5)O_4时的一步法合成二甲醚的催化活性要高于物相为Cu_(1.5)Mn_(1.5)O_4+Mn_2O_3时的活性;在Cu-Zn-Mn/zeolite-Y催化剂中,Mn不仅与Cu作用形成Cu_(1.5)Mn_(1.5)O_4,同时与Zn作用形成ZnMn_2O_4,不仅CuO晶粒粒径变小,而且ZnO的晶粒粒径也变小,催化剂颗粒粒径分布较窄。CuO和ZnO的晶粒的同时减小及相互分散(铜物种和ZnO的紧密接触),使得铜和锌之间的相互作用加强,从而产生更多的活性位。
Mn对Cu-Zn/zeolite-Y催化剂的促进作用的原因主要表现在:在Cu-Zn-Mn/zeolite-Y催化剂前驱体形成过程中可较易使Cu、Zn之间形成异质同晶取代的单斜绿铜锌矿(Cu,Zn)_2(OH)_2CO_3前驱体,同时MnCO_3中也可发生Cu和Zn的掺杂,在随后的焙烧及还原过程中,锰的存在不但有效地保持铜和锌的高度分散和二者较高的紧密接触,同时又提供了合适的化学环境和提高了催化剂的水汽变换性能;
Mn添加方式影响复合催化剂对合成气一步法合成二甲醚的催化活性,通过铜、锌和锰共流沉淀浸渍在zeolite-Y上制得的Cu-Zn-Mn/zeolite-Y催化剂(CZMY-C)的CO加氢活性明显高于先共沉淀铜和锌浸渍后再连续沉淀浸渍锰时制备的Cu-Zn-Mn/zeolite-Y催化剂(CZMY-S)。同时共沉淀浸渍的催化剂CZMY-C的制备过程中,容易形成异质同晶取代的单斜绿铜锌矿(类孔雀石结构)(Cu,Zn)_2(OH)_2CO_3前驱体,焙烧后的催化剂中CuO和ZnO接触更为紧密,其晶粒粒径较小且颗粒分布窄,还原后有更多的Cu-ZnO界面存在,因而Cu与ZnO在催化剂中发挥了更好的协同作用。而分步共沉淀浸渍制备的复合催化剂CZMY-S前驱体主要是由无定形的Cu、Zn碱式碳酸盐组成,高温分解后形成的CuO、ZnO晶粒粒径较大并且颗粒分部较宽,不利于铜锌之间良好的接触和协同作用的发挥。
采用碳酸氢钠作为沉淀剂,或采用碳酸钠为沉淀剂经沉淀充分老化可以制备出高活性的合成气一步法合成二甲醚Cu-Zn/zeolite-Y催化剂,并且二者的活性基本相同,CO的转化率和二甲醚的选择性分别达到77%和66%左右。表征结果发现二者的前驱体中均以异质同晶结构的绿铜锌矿为主,证实了Mn在Cu-Zn-Mn/zeolite-Y催化剂制备过程中对活性前驱体形成的促进作用。
Dimethyl ether(DME) is an important chemical product and potential clean energy,with wide application in many industrial fields.The One-step synthesis of dimethyl ether via syngas is of economic values and theoretical significance,because it is greatly favorable in thermodynamics.In this thesis,we have designed a series of hybrid catalyst by altering methodology of preparation and investigated the hydrogenation properties of those hybrid catalysts.In addition,the effects of Mn promoter and different precursors on the catalytic performance of hybrid Cu-based/zeolite-Y have been systematically studied.
Cu-Mn/zeolite-Y catalysts prepared using a coprecipitation impregnation procedure have been investigated to develop active Cu-based catalysts for the dimethyl ether synthesis from syngas.A great enhancement of CO conversion and DME selectivity is observed on Mn-containing catalysts compared to Mn-free counterpart.However,excess addition of manganese suppresses the syngas-to-dimethyl ether(STD) activity.Manganese has been found to be interacting with copper to form copper manganese mixed oxides phase(Cu_(1+x)Mn_(2-x)O_4) upon calcinations and the excess addition of copper or manganese will induce the segregation of copper or manganese as isolated CuO or Mn_2O_3 phase,respectively. The segregates CuO phases enhanced the reducibility of Cu_(1+x)Mn_(2-x)O_4 phase and Mn_2O_3 phase by reducing spill-over species.Furthermore,it is found that addition of Mn to Cu/zeolite-Y catalyst decreases the average particle size of copper to same extent.Combining the TPR and XRD analysis,it suggests that catalyst with the excess CuO phases in conjunction with copper manganese mixed oxides are much more active than that with excess Mn_2O_3 phases together with copper manganese mixed oxides in the hydrogenation of CO to DME.
The addition of a certain amount of manganese to the Cu-Zn/zeolite-Y catalyst remarkably improves the activity of the catalyst for the direct synthesis of dimethyl ether from syngas.The conversion of CO increases from 56.8%on Cu-Zn/zeolite-Y to 82.9%on Cu-Zn-Mn/zeolite-Y.The characterization of XRD reveals that a pronounced reduction in crystallite size of both CuO and ZnO is observed upon the addition of Mn.Combined with the HRTEM analysis results,it is deduced that the smaller crystallite size of both CuO and ZnO and higher inter-dispersion between the metal oxide components is responsible for the significantly high catalytic activity.A much higher resistance to sintering on Mn-modified than on Mn-free Cu-Zn/zeolite-Y catalyst is also found.
The catalytic activity of Cu-Zn/zeolite-Y catalyst can be promoted by aging the precipitate during the precipitation and it can also be improved significantly by the addition of manganese during the precipitation without the aging process.The remarked increase in the catalytic activity of the MCZY catalyst is explained by that the incorporation of Mn during the co-precipitation process shorten the time of the development of a blue-green precursor,a structure in which the Cu and Zn are atomically dispersed in a hydroxycarbonate matrix.Finally,this leads to ideally mixed and uniformly distributed copper and zinc mixed oxides with smaller particle sizes than the CZY sample derived from independent Cu and Zn precursor phases. Undoubtedly,it appears to be a reasonable explanation for the promoting effect of manganese on the catalytic activity of CZY catalyst in DME synthesis to certain extent
An investigation is carried out to indentify the effects of manganese incorporation sequence on the catalytic structures and performance of Cu-Zn/zeolite-Y Catalyst for direct dimethyl ether synthesis from syngas.Three different catalysts are prepared:the Cu-Zn/zeolite-Y(CZY),and two Mn-promoted Cu-Zn/zeolite-Y Catalysts,MCZY-C and MCZY-S,which are prepared by simultaneous co-precipitation impregnation and sequential precipitation impregnation, respectively.The MCZY-C catalyst appears to be the most active for dimethyl ether synthesis,whereas the MCZY-S catalyst shows little increase in the catalytic activity with respect to the CZ-Y catalyst.The remarked increase in the catalytic activity of the MCZY-C catalyst is explained by that the incorporation of Mn during the simultaneous co-precipitation impregnation process favor the development of a blue-green precursor,a structure in which the Cu and Zn are atomically dispersed in a hydroxycarbonate matrix.Finally,this leads to ideally mixed and uniformly distributed copper and zinc mixed oxides with smaller particle sizes than the other two samples derived from independent Cu and Zn precursor phases.This study reveals significance of the methodology used for the incorporation of manganese. Meanwhile,it shows that the precipitation order has a remarkable influence on the properties of the precursors and calcined catalysts,and consequently,on the catalytic performance for the direct synthesis of dimethyl ether from syngas.
Two different precipitating agents,Na_2CO_3 solution and NaHCO_3 solution,were used to explore the effect of method of preparations on the properties and catalytic perforamance of the catalysts for the dimethyl ether synthesis via syngas.The bi-functional catalysts obtained were investigated as synthesized or after calcination by various physico-chemical techniques.Cu-Zn/zeolite-Y catalyst obtained from the co-precipitation impregnation process using NaHCO_3 was found to be superior to that using Na_2CO_3 solution in terms of activity and stability.The conversion of CO and the selectivity to DME of the catalyst,prepared by using NaHCO_3 solution as precipiating agent,reaches 78.1%and 66.2%,respectively,under the reaction conditions of 2.0 MPa,250℃,1500 h~(-1).Precipitation using sodium carbonate solution leads to the formation of an amorphous phase precursor whereas using NaHCO_3 results in a high-zincian malachite phase.Finally,smaller crystallite size of Cu and ZnO and higher microstrain of copper particle are found in calcined Cu-Zn/zeoltie-Y catalyst prepared by using NaHCO_3 solution.Therefore,the increase in the activity and stability of the catalyst prepared by using NaHCO_3 solution as precipiating agent do not only correlate with the specific Cu surface area but also coincides with an increase in the microstrain in the metallic copper presumably because of the improved contact area(interfacial area) between Cu and ZnO.Based on the characterization data,it has shown that the selection of a suitable precipitating agent for the Cu-Zn/zeoltie-Y catalyst preparation via co-precipitation impregnation process significantly influences the properties of the precursors and therefore the formation of the final structure and catalytic activity.
采用相同的共沉淀浸渍法制备了不同组成和组分配比的Cu-Mn/zeolite-Y、Cu-Zn/zeolite-Y和Cu-Zn-Mn/zeolite-Y系列催化剂,通过对其反应性能的考察,发现Cu-Mn/zeolite-Y催化剂虽然低温活性不够高,但其合成二甲醚反应的稳定性较好;调节Cu/Zn比可获得较高催化活性的Cu-Zn/zeolite-Y催化剂,但其稳定性不高;Cu-Zn-Mn/zeolite-Y催化剂与Cu-Zn/zeolite-Y催化剂相比,其催化活性和稳定性有很大的提高,CO转化率从58.5%增加到82.9%,并且对于Cu-Zn-Mn/zeolite-Y催化剂体系,Cu、Zn和Mn的含量在较宽的范围内,并不影响催化剂的合成二甲醚活性。
在Cu-Mn/zeolite-Y催化剂中,Cu与Mn之间可形成类尖晶石复合氧化物Cu_(1.5)Mn_(1.5)O_4,并且当催化剂的物相组成为CuO+Cu_(1.5)Mn_(1.5)O_4时的一步法合成二甲醚的催化活性要高于物相为Cu_(1.5)Mn_(1.5)O_4+Mn_2O_3时的活性;在Cu-Zn-Mn/zeolite-Y催化剂中,Mn不仅与Cu作用形成Cu_(1.5)Mn_(1.5)O_4,同时与Zn作用形成ZnMn_2O_4,不仅CuO晶粒粒径变小,而且ZnO的晶粒粒径也变小,催化剂颗粒粒径分布较窄。CuO和ZnO的晶粒的同时减小及相互分散(铜物种和ZnO的紧密接触),使得铜和锌之间的相互作用加强,从而产生更多的活性位。
Mn对Cu-Zn/zeolite-Y催化剂的促进作用的原因主要表现在:在Cu-Zn-Mn/zeolite-Y催化剂前驱体形成过程中可较易使Cu、Zn之间形成异质同晶取代的单斜绿铜锌矿(Cu,Zn)_2(OH)_2CO_3前驱体,同时MnCO_3中也可发生Cu和Zn的掺杂,在随后的焙烧及还原过程中,锰的存在不但有效地保持铜和锌的高度分散和二者较高的紧密接触,同时又提供了合适的化学环境和提高了催化剂的水汽变换性能;
Mn添加方式影响复合催化剂对合成气一步法合成二甲醚的催化活性,通过铜、锌和锰共流沉淀浸渍在zeolite-Y上制得的Cu-Zn-Mn/zeolite-Y催化剂(CZMY-C)的CO加氢活性明显高于先共沉淀铜和锌浸渍后再连续沉淀浸渍锰时制备的Cu-Zn-Mn/zeolite-Y催化剂(CZMY-S)。同时共沉淀浸渍的催化剂CZMY-C的制备过程中,容易形成异质同晶取代的单斜绿铜锌矿(类孔雀石结构)(Cu,Zn)_2(OH)_2CO_3前驱体,焙烧后的催化剂中CuO和ZnO接触更为紧密,其晶粒粒径较小且颗粒分布窄,还原后有更多的Cu-ZnO界面存在,因而Cu与ZnO在催化剂中发挥了更好的协同作用。而分步共沉淀浸渍制备的复合催化剂CZMY-S前驱体主要是由无定形的Cu、Zn碱式碳酸盐组成,高温分解后形成的CuO、ZnO晶粒粒径较大并且颗粒分部较宽,不利于铜锌之间良好的接触和协同作用的发挥。
采用碳酸氢钠作为沉淀剂,或采用碳酸钠为沉淀剂经沉淀充分老化可以制备出高活性的合成气一步法合成二甲醚Cu-Zn/zeolite-Y催化剂,并且二者的活性基本相同,CO的转化率和二甲醚的选择性分别达到77%和66%左右。表征结果发现二者的前驱体中均以异质同晶结构的绿铜锌矿为主,证实了Mn在Cu-Zn-Mn/zeolite-Y催化剂制备过程中对活性前驱体形成的促进作用。
Dimethyl ether(DME) is an important chemical product and potential clean energy,with wide application in many industrial fields.The One-step synthesis of dimethyl ether via syngas is of economic values and theoretical significance,because it is greatly favorable in thermodynamics.In this thesis,we have designed a series of hybrid catalyst by altering methodology of preparation and investigated the hydrogenation properties of those hybrid catalysts.In addition,the effects of Mn promoter and different precursors on the catalytic performance of hybrid Cu-based/zeolite-Y have been systematically studied.
Cu-Mn/zeolite-Y catalysts prepared using a coprecipitation impregnation procedure have been investigated to develop active Cu-based catalysts for the dimethyl ether synthesis from syngas.A great enhancement of CO conversion and DME selectivity is observed on Mn-containing catalysts compared to Mn-free counterpart.However,excess addition of manganese suppresses the syngas-to-dimethyl ether(STD) activity.Manganese has been found to be interacting with copper to form copper manganese mixed oxides phase(Cu_(1+x)Mn_(2-x)O_4) upon calcinations and the excess addition of copper or manganese will induce the segregation of copper or manganese as isolated CuO or Mn_2O_3 phase,respectively. The segregates CuO phases enhanced the reducibility of Cu_(1+x)Mn_(2-x)O_4 phase and Mn_2O_3 phase by reducing spill-over species.Furthermore,it is found that addition of Mn to Cu/zeolite-Y catalyst decreases the average particle size of copper to same extent.Combining the TPR and XRD analysis,it suggests that catalyst with the excess CuO phases in conjunction with copper manganese mixed oxides are much more active than that with excess Mn_2O_3 phases together with copper manganese mixed oxides in the hydrogenation of CO to DME.
The addition of a certain amount of manganese to the Cu-Zn/zeolite-Y catalyst remarkably improves the activity of the catalyst for the direct synthesis of dimethyl ether from syngas.The conversion of CO increases from 56.8%on Cu-Zn/zeolite-Y to 82.9%on Cu-Zn-Mn/zeolite-Y.The characterization of XRD reveals that a pronounced reduction in crystallite size of both CuO and ZnO is observed upon the addition of Mn.Combined with the HRTEM analysis results,it is deduced that the smaller crystallite size of both CuO and ZnO and higher inter-dispersion between the metal oxide components is responsible for the significantly high catalytic activity.A much higher resistance to sintering on Mn-modified than on Mn-free Cu-Zn/zeolite-Y catalyst is also found.
The catalytic activity of Cu-Zn/zeolite-Y catalyst can be promoted by aging the precipitate during the precipitation and it can also be improved significantly by the addition of manganese during the precipitation without the aging process.The remarked increase in the catalytic activity of the MCZY catalyst is explained by that the incorporation of Mn during the co-precipitation process shorten the time of the development of a blue-green precursor,a structure in which the Cu and Zn are atomically dispersed in a hydroxycarbonate matrix.Finally,this leads to ideally mixed and uniformly distributed copper and zinc mixed oxides with smaller particle sizes than the CZY sample derived from independent Cu and Zn precursor phases. Undoubtedly,it appears to be a reasonable explanation for the promoting effect of manganese on the catalytic activity of CZY catalyst in DME synthesis to certain extent
An investigation is carried out to indentify the effects of manganese incorporation sequence on the catalytic structures and performance of Cu-Zn/zeolite-Y Catalyst for direct dimethyl ether synthesis from syngas.Three different catalysts are prepared:the Cu-Zn/zeolite-Y(CZY),and two Mn-promoted Cu-Zn/zeolite-Y Catalysts,MCZY-C and MCZY-S,which are prepared by simultaneous co-precipitation impregnation and sequential precipitation impregnation, respectively.The MCZY-C catalyst appears to be the most active for dimethyl ether synthesis,whereas the MCZY-S catalyst shows little increase in the catalytic activity with respect to the CZ-Y catalyst.The remarked increase in the catalytic activity of the MCZY-C catalyst is explained by that the incorporation of Mn during the simultaneous co-precipitation impregnation process favor the development of a blue-green precursor,a structure in which the Cu and Zn are atomically dispersed in a hydroxycarbonate matrix.Finally,this leads to ideally mixed and uniformly distributed copper and zinc mixed oxides with smaller particle sizes than the other two samples derived from independent Cu and Zn precursor phases.This study reveals significance of the methodology used for the incorporation of manganese. Meanwhile,it shows that the precipitation order has a remarkable influence on the properties of the precursors and calcined catalysts,and consequently,on the catalytic performance for the direct synthesis of dimethyl ether from syngas.
Two different precipitating agents,Na_2CO_3 solution and NaHCO_3 solution,were used to explore the effect of method of preparations on the properties and catalytic perforamance of the catalysts for the dimethyl ether synthesis via syngas.The bi-functional catalysts obtained were investigated as synthesized or after calcination by various physico-chemical techniques.Cu-Zn/zeolite-Y catalyst obtained from the co-precipitation impregnation process using NaHCO_3 was found to be superior to that using Na_2CO_3 solution in terms of activity and stability.The conversion of CO and the selectivity to DME of the catalyst,prepared by using NaHCO_3 solution as precipiating agent,reaches 78.1%and 66.2%,respectively,under the reaction conditions of 2.0 MPa,250℃,1500 h~(-1).Precipitation using sodium carbonate solution leads to the formation of an amorphous phase precursor whereas using NaHCO_3 results in a high-zincian malachite phase.Finally,smaller crystallite size of Cu and ZnO and higher microstrain of copper particle are found in calcined Cu-Zn/zeoltie-Y catalyst prepared by using NaHCO_3 solution.Therefore,the increase in the activity and stability of the catalyst prepared by using NaHCO_3 solution as precipiating agent do not only correlate with the specific Cu surface area but also coincides with an increase in the microstrain in the metallic copper presumably because of the improved contact area(interfacial area) between Cu and ZnO.Based on the characterization data,it has shown that the selection of a suitable precipitating agent for the Cu-Zn/zeoltie-Y catalyst preparation via co-precipitation impregnation process significantly influences the properties of the precursors and therefore the formation of the final structure and catalytic activity.
引文
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