560
A fundamental approach for the catalytic synthesis of methanol was given by
Paul Sabatier in the 1920s. According to Sabatier and group, methanol was synthesized over Ni-based catalyst by hydrogenation of functional groups [11]. Thereafter,
breakthrough catalyst was developed, and first industrial process for methanol production was established by BASF in Germany [12]. Catalyst used in the same process was of zinc oxide and chromate based. This catalyst was not that active and
thus required a very high temperature (300–400 °C). This is a high-pressure favorable reaction due to exothermic and compressing volume nature of reaction. Pressure
required was 250–350 bar along with high temperature of 300–400 °C [13–16].
This breakthrough technology was dominated in the market over 50 years, and
exportation of process was started by DuPont and commercial solvents corporation
in the United States. Besides, improvements in the operating conditions (temperature, pressure) have sought the attention of research community worldwide. In the
1940s, the Swiss Lonza Company started the methanol formation from electrolytic
hydrogen and carbon oxides. Following this, Prof. Natta suggested catalytic hydrogenation of purified syngas over ZnO-based catalyst. Feedstocks (CO, CO 2 , and H 2 )
were purified by vapors of calcium nitrates to increase the production and selectivity of methanol [17].
In the 1966s, important discovery was found in imperial chemical industries.
According to this, drastic change was observed in the catalyst formulation, operating conditions, and quality of syngas. Catalyst was copper based and was found
more efficient than ZnO-based catalyst but even more prone to deactivation by sulfur impurities present in the coal-gasified syngas. Operating conditions were
reduced up to 300 °C and 100 bar, and purer syngas was obtained from the steam
reforming of methane or from natural gas and naphtha feedstocks. Since then, the
so-called low-temperature, low-pressure ICI process was applied for methanol synthesis in industries [10]. On this basis, in the 1970s, many plants such as Lurgi,
Haldor Topsoe, and Linde have been established for methanol production from purified syngas. A lot of investigations and efforts have been done for developing even
lower temperature and pressure process. All the abovementioned plants are currently running at 250–300 °C and 50 bar over Cu-/ZnO-based catalyst [18] (Fig. 2).
A consolidated quick description of how methanol synthesis has evolved over a
period of time has been given in Table 1.
1.2 Primary Reactions for Methanol Synthesis
Methanol is one of the utmost essential commodities and building block chemicals
in today’s world. Since 1960, more than 90 production plants with production
capacity of 110 metric tons (MTs) have been established to meet the rise in global
demand of 70 MTs [10]. Apart from being used as a fuel, methanol can also be used
as a raw material for the production of olefins and paraffins and serves as a key
intermediate for production of many other industrially relevant chemicals like formaldehyde, methyl tert-butyl ether, and acetic acid [19]. It also finds application as a
K. Tripathi et al.
A fundamental approach for the catalytic synthesis of methanol was given by
Paul Sabatier in the 1920s. According to Sabatier and group, methanol was synthesized over Ni-based catalyst by hydrogenation of functional groups [11]. Thereafter,
breakthrough catalyst was developed, and first industrial process for methanol production was established by BASF in Germany [12]. Catalyst used in the same process was of zinc oxide and chromate based. This catalyst was not that active and
thus required a very high temperature (300–400 °C). This is a high-pressure favorable reaction due to exothermic and compressing volume nature of reaction. Pressure
required was 250–350 bar along with high temperature of 300–400 °C [13–16].
This breakthrough technology was dominated in the market over 50 years, and
exportation of process was started by DuPont and commercial solvents corporation
in the United States. Besides, improvements in the operating conditions (temperature, pressure) have sought the attention of research community worldwide. In the
1940s, the Swiss Lonza Company started the methanol formation from electrolytic
hydrogen and carbon oxides. Following this, Prof. Natta suggested catalytic hydrogenation of purified syngas over ZnO-based catalyst. Feedstocks (CO, CO 2 , and H 2 )
were purified by vapors of calcium nitrates to increase the production and selectivity of methanol [17].
In the 1966s, important discovery was found in imperial chemical industries.
According to this, drastic change was observed in the catalyst formulation, operating conditions, and quality of syngas. Catalyst was copper based and was found
more efficient than ZnO-based catalyst but even more prone to deactivation by sulfur impurities present in the coal-gasified syngas. Operating conditions were
reduced up to 300 °C and 100 bar, and purer syngas was obtained from the steam
reforming of methane or from natural gas and naphtha feedstocks. Since then, the
so-called low-temperature, low-pressure ICI process was applied for methanol synthesis in industries [10]. On this basis, in the 1970s, many plants such as Lurgi,
Haldor Topsoe, and Linde have been established for methanol production from purified syngas. A lot of investigations and efforts have been done for developing even
lower temperature and pressure process. All the abovementioned plants are currently running at 250–300 °C and 50 bar over Cu-/ZnO-based catalyst [18] (Fig. 2).
A consolidated quick description of how methanol synthesis has evolved over a
period of time has been given in Table 1.
1.2 Primary Reactions for Methanol Synthesis
Methanol is one of the utmost essential commodities and building block chemicals
in today’s world. Since 1960, more than 90 production plants with production
capacity of 110 metric tons (MTs) have been established to meet the rise in global
demand of 70 MTs [10]. Apart from being used as a fuel, methanol can also be used
as a raw material for the production of olefins and paraffins and serves as a key
intermediate for production of many other industrially relevant chemicals like formaldehyde, methyl tert-butyl ether, and acetic acid [19]. It also finds application as a
K. Tripathi et al.