Major Project Draft#2

High performance Cu–ZnO/Pd-b catalysts for syngas to LPG

Ge et al. (2008) conducted a performance study of Cu (Copper)/ZnO (Zinc oxide) over Pd (Palladium)-b (beta-zeolite) for preparation by physical mixing. They investigated Cu-ZnO/Pd-bzeolite because Cu strongly inhibits coke formation, ZnO was helped dispersion of Cu in catalyst, Pd-b was showed the best activity for conversion methanol to LPG. In this research, they studied different kinds of zeolites, influence of SiO₂/Al₂O₃ ratio, crystal size b of catalyst, influence of Pd content on catalyst, and optimum condition for synthesis LPG from syngas. After preparation,  the catalyst was analyzed by X-ray Diffraction (XRD) for the study crystal size of catalyst, Scanning Electron Microscope (SEM) for the study crystal of catalyst, and H₂-chemisorption. From the results found that Cu-ZnO/Pd-b was higher conversed methanol to LPG than Cu-ZnO/Pd-ZSM-5, and Cu-ZnO/Pd-UDY, due to Cu-ZnO/Pd-b showed the high activity by CO conversion achieve 72.9%. The SiO₂/Al₂O₃ ratio was at 37 which shown high CO conversion because acidic active site of catalyst increasing by CO conversion achieve 72.2%. The crystal size b at (2) was showed high CO conversion because this size have small crystal. The Pd content at 0.2 wt% was showed high CO conversion. For optimum condition at the study found that at temperature 325 °C and pressure 2.1 MPa was showed high CO conversion and yield of hydrocarbon. Additionally, properties of Cu-ZnO/Pd-b catalyst was significantly improved comparing with other catalyst. The researcher suggested that Cu-ZnO/Pd-b might be used for synthesis LPG from methanol due to its high activity and high yield hydrocarbon.

            This study provides helping the conversion of methanol to LPG with high performance and environmentally friendly. However, this catalyst is some limitation.

1)               The researcher did not study durable, and specific surface area of Cu-ZnO/Pd-b catalyst. The researcher might miss effect related to activity of catalyst. Actually, the catalyst should be studied durable and specific surface area of catalysts. For Example, Congming Li et al. (2014) study durable, and specific surface area of CZZA/Pd-b catalyst. The results found that CZZA/Pd-b catalyst could be operate 100 hours by this catalyst without regenerate coke on catalyst. The specific surface area of CZZA/Pd-b catalyst is 17.4 square metres per gram.

2)         This study did not investigate mechanism of reaction, by mechanism should be studied major topic, which is important for the study effect of metal on catalyst. All catalyst should be studied because when they added metal on catalyst found that the product and byproduct from reaction not coincide. Then, they known the effect of metal to reaction (Li et al., 2014).

3)         This study used only SEM to confirm the dispersion of metal on catalyst. The researcher should be studied dispersion by other technique to confirm the presence of Cu, ZnO, and Pd metal on catalyst.  One of common method for the study dispersion of catalyst is Energy-dispersive X-ray spectroscopy (EDX) technique. Using a combination of SEM is more performance for analyzer catalyst than using only one this method (Li et al., 2014).

            The strength of this study is that the ratio of catalyst, component and optimum condition.These method are widely major problem of catalyst is coke formation on catalyst. Another advantage of this study is that the product from reaction could be decreased LPG from crude oil.  

References

Qingjie Ge, Yu Lian, Xingdong Yuan, Xiaohong Li, Kaoru Fujimoto (2008). High performance Cu– ZnO/Pd-b catalysts for syngas to LPG. Catalysis Communications, 9, 256–261

Congming Li, Xingdong Yuan, Kaoru Fujimoto (2014). Development of highly stable catalyst for methanol synthesis from carbon dioxide. Applied Catalysis A: General, 469, 306– 311

Major Project

High performance Cu–ZnO/Pd-b catalysts for syngas to LPG

Qingjie et al. (2008) conducted a performance study of Cu (Copper)/ZnO (Zinc oxide) over Pd (Palladium)-b (beta-zeolite) for preparation by physically mixing. They investigated Cu-ZnO/Pd-b zeolite because Cu strongly inhibits coke formation, ZnO was helped dispersion of Cu in catalyst, Pd-b was showed the best activity for conversion methanol to LPG. In this research, they studied different kinds of zeolites, influence of SiO₂/Al₂O₃ ratio, crystal size b of catalyst, influence of Pd content on catalyst, and optimum condition for synthesis LPG from syngas. After preparation,  the catalyst will analyzed by X-ray Diffraction (XRD) for the study crystal size of catalyst, Scanning Electron Microscope (SEM) for looking crystal of catalyst, and H₂-chemisorption. From the results found that Cu-ZnO/Pd-b was higher conversed methanol to LPG than Cu-ZnO/Pd-ZSM-5, and Cu-ZnO/Pd-UDY due to Cu-ZnO/Pd-b showed the high activity by CO conversion achieve 72.9%.  The SiO₂/Al₂O₃ ratio at 37 was showed high CO conversion because acidic active site of catalyst increasing by CO conversion achieve 72.2%. The crystal size b at (2) was showed high CO conversion because this size have small crystal size. The Pd content at 0.2 wt% was showed high CO conversion. For optimum condition at the study found that at temperature 325 °C and pressure 2.1 MPa was showed high CO conversion and yield of hydrocarbon. Additionally, properties of Cu-ZnO/Pd-b catalyst was significantly improved comparing with other catalyst. The researcher suggested that Cu-ZnO/Pd-b might be used for synthesis LPG from methanol due to its high activity and high yield hydrocarbon.

            This study provides helping the conversion of methanol to LPG with high performance and environmentally friendly. However, this catalyst is some limitation.

1)               The researcher did not study durable, and specific surface area of Cu-ZnO/Pd-b catalyst. The researcher might miss effect related to activity of catalyst. Actually, the catalyst should be studied durable and specific surface area of catalysts. For Example, Congming Li et al. (2014) study durable, and specific surface area of CZZA/Pd-b catalyst. The results found that CZZA/Pd-b catalyst could be operate 100 hours by this catalyst without regenerate coke on catalyst. The specific surface area of CZZA/Pd-b catalyst is 17.4 square metres per gram.

2)         This study did not investigate mechanism of reaction, by mechanism should be studied major topic, which is important for the study effect of metal on catalyst. All catalyst should be studied because when they added metal on catalyst found that the product and byproduct from reaction not coincide. Then, they known the effect of metal to reaction (Congming Li et al., 2014).

3)         This study used only SEM to confirm the dispersion of metal on catalyst. The researcher should be studied dispersion by other technique to confirm the presence of Cu, ZnO, and Pd metal on catalyst.  One of common method for the study dispersion of catalyst is Energy-dispersive X-ray spectroscopy (EDX) technique. Using a combination of SEM is more performance for analyzer catalyst than using only one this method (Congming Li et al., 2014).

            The strength of this study is that the ratio of catalyst, component and optimum condition. These method are widely major problem of catalyst is coke formation on catalyst. Another advantage of this study is that the product from reaction could be decreased LPG from crude oil.  

References

Qingjie Ge, Yu Lian, Xingdong Yuan, Xiaohong Li, Kaoru Fujimoto (2008). High performance Cu– ZnO/Pd-b catalysts for syngas to LPG. Catalysis Communications, 9, 256–261

Congming Li, Xingdong Yuan, Kaoru Fujimoto (2014). Development of highly stable catalyst for methanol synthesis from carbon dioxide. Applied Catalysis A: General, 469, 306– 311

Minor Project

Minor Project

My research question is high volume of carbon monoxide (CO) and carbon dioxide (CO₂) affect greenhouse effect in the world. How we will eliminate it or we will destroy it. Then CO and CO₂ will destroy atmosphere of earth and affect increasing temperature some research say it is very important.

Researchers who have looked at this subject are Qingjie Ge and Congming Li. They changed CO and CO₂ to LPG, chemical or high value product. They argue that this method used catalyst. It would help decreasing the amount of carbon monoxide, carbon dioxide and decreasing greenhouse effect within the world. 

Qingjie et al. (2008) argued that performance Cu–ZnO/Pd-B catalyst has been investigated under the suitable conditions, catalyst exhibit an excellent catalytic performance for syngas to LPG.

Congming et al. (2014) argued that hybrid catalysts consisting of Zr-Cu–Zn catalyst with Pd-B zeolite were found to show high and stable conversion for CO₂ hydrogenation.

Debate centers on the issue of Qingjie and Congming. The selectivity and conversion of catalyst was changed CO and CO₂ to LPG less than 75%

There is still work to be done on my research will improve catalyst with increasing selectivity and conversion of CO and CO₂ more than 90%

My research will be closest to Qingjie and Congming because I will add the other metal such as Ni, Mo, Ce, Pt, Au and etc into Cu–ZnO/Pd-B catalyst with increasing effective and stability of catalyst to high conversion. The catalyst will used for conversion CO and CO₂ to LPG.

Hopefully, my research will help to improve increasing effective and stability of catalyst and it also help to converse CO and CO₂ to LPG more than 95% when compared with previous catalyst and the product from reaction will get LPG only by the byproduct will not have obtained from reaction.

Reference List

Qingjie, G., Yu, L., Xingdong, Y., Xiaohong, L., & Kaoru, F. (2008). High performance           ZnO/Pd-B catalysts for syngas to LPG. Catalysis Communications, 9, 256–261.

Congming, L., Xingdong, Y., & Kaoru, F. (2014). Direct synthesis of LPG from carbon              dioxide over hybrid catalysts comprising modified methanol synthesis catalyst                and B-type zeolite. Applied Catalysis A: General, 475, 155–160.

Assignment2: Writing an introduction

The conversion carbon dioxide to LPG over hybrid catalysts by synthesis catalyst and B-type zeolite

by

Panya Wattanapaphawong

Stage 1: Carbon dioxide is one of the most abundant and widely distributed carbon resources, and has become the focus of attention because of its greenhouse effects. Therefore, the utilization of carbon dioxide is desirable for the effective method for reducing carbon dioxide emission. Many kinds of strategies with this regard have been proposed to solve this intractable problem (L. Congming et al., 2014). Liquefied Petroleum Gas (LPG), a mixture of propane and butanes, has environmentally benign characteristics and widely been used as clean fuels. Direct synthesis of LPG from syngas is an important choice for converting natural gas to high-value-added products (G. Qingjie et al., 2007).

Stage 2: Many previous studies have reported on the utilization of carbon dioxide for synthesis LPG or chemical. According to Qingjie et al. (2007), they study effect of Cu-ZnO over B-zeolite found that under the suitable conditions, Cu–ZnO/Pd-b catalyst exhibit an excellent catalytic performance for carbon dioxide to LPG: 72.2%. Kenji Asami et al. (2005) reported Co-Mo-Ni in hybrid catalyst could restrain the decomposition of DME into carbon dioxide, but the DME conversion and selectivity for LPG were not high. L. Congming et al. (2014) reported Hybrid catalysts consisting of Zr modified Cu–Zn catalyst with Pd-modified B-zeolite were found to show high and stable conversion for carbon dioxide hydrogenation. The stable activity of carbon dioxide conversion can be attributed to the high water resistant of CZZA. The hybrid catalyst consisting of CZZA with Pd-B was effective for LPG synthesis with selectivity as high as 75%.

Stage 3: From literature review found that the condition of carbon dioxide conversion to LPG was high condition such as high temperature, high pressure etc.

Stage 4&5: In this research work will study catalyst of conversion carbon dioxide to LPG at low condition and study condition of new catalyst. The selectivity of LPG as high as 90%.  

Assignment 1: Citation

Direct synthesis of LPG from carbon dioxide over hybrid catalysts comprising modified methanol synthesis catalyst and B-type zeolite

Abstract

Hydrogenation of carbon dioxide to C3 and C4 paraffins (LPG) was studied by using hybrid catalysts composed of Zr-modified Cu–Zn catalyst with Pd-modified zeolite. Various factors that affect catalyst activity, including reaction temperature, space velocity, pressure, and the ratio of H2 to CO2 were investigated thoroughly. The hybrid catalysts exhibited stable activity over 100 h and extraordinary high selectivity of LPG synthesis (especially iso-butane) even under low temperature (260◦C) and low pressure (2 MPa). Conversion of CO2 and the yield of hydrocarbon reached 25.2% and 13.3%, respectively, while keeping the selectivity of LPG and CH4 75% and 1%, respectively. The iso-butane/n-butane ratio was about 16/1, whose value was much higher than that of thermodynamic equilibrium (about 1/1).

Reference

Congming Li, Xingdong Yuan, Kaoru Fujimoto (2014). Direct synthesis of LPG from carbon dioxide over hybrid catalysts comprising modified methanol synthesis catalyst and B -type zeolite. Applied Catalysis A: General, 475, 155–160.

Results and findings

- Hybrid catalysts consisting of Zr modified Cu–Zn catalyst with Pd-modified zeolite were found to show high and stable conversion for CO2 hydrogenation.

- The stable activity of CO2 conversion can be attributed to the high water resistant of CZZA.

-The hybrid catalyst consisting of CZZA with Pd-B was effective for LPG synthesis with selectivity as high as 75% and with little methane formation.

- The Catalytic activity was stable over 100 h.

Citations

- Congming Li, Xingdong Yuan, Kaoru Fujimoto (2014) reported that The conversion carbon dioxide  to LPG over B-type zeolite catalyst (155-160).

- According to Congming Li, Xingdong Yuan, Kaoru Fujimoto (2014), Direct synthesis of LPG from carbon dioxide by using hybrid catalysts comprising modified methanol synthesis B- type zeolite catalyst (155-160).