3.6 Summary
67
methanol derivatives requires hydrolysis and is hence disadvantageous. Further, in
addition to the use of highly corrosive substances such as sulfuric acid and trifluoroacetic acid, the use of hydrolysis processes can be a major problem in the methanol
synthesis process from methane via methanol derivatives.
On the other hand, the “methanol protection” strategy undertaken in the conversion to methanol derivatives suggests an important direction of research toward the
development of practical applications for methanol synthesis from methane [90].
For example, the physical separation of methanol from a reaction mixture using a
membrane can be considered for adapting to methanol production reactions. The
membrane separation technique is also being studied in the production of methanol
from methane using biocatalysts [93–95]. Also, other methanol protection strategies
such as the use of chemical loops in the methane conversion with metal ion-exchanged
zeolites and the use of multicomponent catalysts for the protection of methanol
have been reported. Overall, approaches to both the catalytic reactions for the direct
synthesis of methanol from methane and other approaches for methanol production
from a broader perspective are essential for enabling potential breakthroughs in the
development of artificial catalysts for conversion of methane to methanol.
References
1. Spencer ND (1988) Partial oxidation of methane to formaldehyde by means of molecular
oxygen. J Catal 109:187–197
2. Spencer ND, Pereira CJ (1989) V 2 O 5 -SiO 2 -catalyzed methane partial oxidation with molecular
oxygen. J Catal 116:399–406
3. Liu HF, Li RS, Liew KY, Johnson RE, Lunsford JH (1984) Partial oxidation of methane by
nitrous oxide over molybdenum on silica. J Am Chem Soc 106:4117–4121
4. Caceres CV, Fierro JLG, Lopez Agudo A, Blanco MN, Thomas HJ (1985) Preparation and
characterization of equilibrium adsorption-prepared molybdena-alumina catalysts. J Catal
95:501–511
5. Kobayashi T, Guilhaume N, Miki J, Kitamura N, Haruta M (1996) Oxidation of methane to
formaldehyde over FeSiO 2 and Sn-W mixed oxides. Catal Today 32:171–175
6. Michalkiewicz B (2004) Partial oxidation of methane to formaldehyde and methanol using
molecular oxygen over Fe-ZSM-5. Appl Catal A: Gen 277:147–153
7. Zhang Q, Li Y, An D, Wang Y (2009) Catalytic behavior and kinetic features of FeOx/SBA-15
catalyst for selective oxidation of methane by oxygen. Appl Catal A: Gen 356:103–111
8. Arena F, Gatti G, Martra G, Coluccia S, Stievano L, Spadaro L, Famulari P, Parmaliana A (2005)
Structure and reactivity in the selective oxidation of methane to formaldehyde of low-loaded
FeO x /SiO 2 catalysts. J Catal 231:365–380
9. He J, Li Y, An D, Zhang Q, Wang Y (2009) Selective oxidation of methane to formaldehyde
by oxygen over silica-supported iron catalysts. J Nat Gas Chem 18:288–294
10. Otsuka K, Wang Y (2001) Direct conversion of methane into oxygenates. Appl Catal A: Gen
222:145–161
11. Wang Y (2006) Selective oxidation of hydrocarbons catalyzed by iron-containing heterogeneous catalysts. Res Chem Intermed 32:235–251
12. McCormick RL, Alptekin GO (2000) Comparison of alumina-, silica-, titania-, and zirconiasupported FePO 4 catalysts for selective methane oxidation. Catal Today 55:269–280
67
methanol derivatives requires hydrolysis and is hence disadvantageous. Further, in
addition to the use of highly corrosive substances such as sulfuric acid and trifluoroacetic acid, the use of hydrolysis processes can be a major problem in the methanol
synthesis process from methane via methanol derivatives.
On the other hand, the “methanol protection” strategy undertaken in the conversion to methanol derivatives suggests an important direction of research toward the
development of practical applications for methanol synthesis from methane [90].
For example, the physical separation of methanol from a reaction mixture using a
membrane can be considered for adapting to methanol production reactions. The
membrane separation technique is also being studied in the production of methanol
from methane using biocatalysts [93–95]. Also, other methanol protection strategies
such as the use of chemical loops in the methane conversion with metal ion-exchanged
zeolites and the use of multicomponent catalysts for the protection of methanol
have been reported. Overall, approaches to both the catalytic reactions for the direct
synthesis of methanol from methane and other approaches for methanol production
from a broader perspective are essential for enabling potential breakthroughs in the
development of artificial catalysts for conversion of methane to methanol.
References
1. Spencer ND (1988) Partial oxidation of methane to formaldehyde by means of molecular
oxygen. J Catal 109:187–197
2. Spencer ND, Pereira CJ (1989) V 2 O 5 -SiO 2 -catalyzed methane partial oxidation with molecular
oxygen. J Catal 116:399–406
3. Liu HF, Li RS, Liew KY, Johnson RE, Lunsford JH (1984) Partial oxidation of methane by
nitrous oxide over molybdenum on silica. J Am Chem Soc 106:4117–4121
4. Caceres CV, Fierro JLG, Lopez Agudo A, Blanco MN, Thomas HJ (1985) Preparation and
characterization of equilibrium adsorption-prepared molybdena-alumina catalysts. J Catal
95:501–511
5. Kobayashi T, Guilhaume N, Miki J, Kitamura N, Haruta M (1996) Oxidation of methane to
formaldehyde over FeSiO 2 and Sn-W mixed oxides. Catal Today 32:171–175
6. Michalkiewicz B (2004) Partial oxidation of methane to formaldehyde and methanol using
molecular oxygen over Fe-ZSM-5. Appl Catal A: Gen 277:147–153
7. Zhang Q, Li Y, An D, Wang Y (2009) Catalytic behavior and kinetic features of FeOx/SBA-15
catalyst for selective oxidation of methane by oxygen. Appl Catal A: Gen 356:103–111
8. Arena F, Gatti G, Martra G, Coluccia S, Stievano L, Spadaro L, Famulari P, Parmaliana A (2005)
Structure and reactivity in the selective oxidation of methane to formaldehyde of low-loaded
FeO x /SiO 2 catalysts. J Catal 231:365–380
9. He J, Li Y, An D, Zhang Q, Wang Y (2009) Selective oxidation of methane to formaldehyde
by oxygen over silica-supported iron catalysts. J Nat Gas Chem 18:288–294
10. Otsuka K, Wang Y (2001) Direct conversion of methane into oxygenates. Appl Catal A: Gen
222:145–161
11. Wang Y (2006) Selective oxidation of hydrocarbons catalyzed by iron-containing heterogeneous catalysts. Res Chem Intermed 32:235–251
12. McCormick RL, Alptekin GO (2000) Comparison of alumina-, silica-, titania-, and zirconiasupported FePO 4 catalysts for selective methane oxidation. Catal Today 55:269–280