Development of a High Performance Photocatalytic Reactor System for the Production of Methanol from Methane in the Gas Phase

EPA Grant Number: R825370C073
Subproject: this is subproject number 073 , established and managed by the Center Director under grant R825370
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).

Center: EERC - National Center for Clean Industrial and Treatment Technologies (CenCITT)
Center Director: Crittenden, John C.
Title: Development of a High Performance Photocatalytic Reactor System for the Production of Methanol from Methane in the Gas Phase
Investigators: Hand, David W. , Crittenden, John C. , Perram, D. L. , Chen, Yongsheng
Institution: Michigan Technological University
EPA Project Officer: Klieforth, Barbara I
Project Period: January 1, 1997 through January 1, 1999
RFA: Exploratory Environmental Research Centers (1992) RFA Text |  Recipients Lists
Research Category: Center for Clean Industrial and Treatment Technologies (CenCITT) , Targeted Research


The goal of this project is to investigate the potential of TiO2 catalysts for a low temperature and low pressure chemical synthesis route to convert methane to methanol and to design a laboratory separative reactor system that can convert methane to methanol for use as a commercial grade feed.


The investigators developed high performance photocatalytic catalysts using surface modifications such as metal semiconductor modification, surface sensitization, and transition metal doping. Conversion to the desired product methanol is adversely affected by further oxidation of methanol to species such as carbon monoxide or carbon dioxide, and this tendency must be reduced. One strategy for reducing this tendency is to remove the methanol from the reactive environment immediately upon formation. This photocatalytic separative reactor system for partial oxidation of methane to methanol will be developed in this project.

The energy requirements for conversion of methane to methanol using different processes including electrochemical process, solar process, and lamp process have been calculated. The energy required for production of one mole methanol from methane is 4.5 einstein (at 365nm).

The photoreactor system made from M7 tubing and quartz tubing has been designed, built and preliminarily tested. The results in the fixed bed photoreactor system showed that the methane conversion, catalyst activity, and quantum efficiency were 8.2%, 2.935 mmol/g/min, and 49.5% respectively. Experiments are ongoing to increase the conversion rate and selectivity by optimizing the CH4/O2 ratio at influent stream, the relative humidity, the empty bed contact time (EBCT), and the reaction temperature, and by cycling the lights on and off to remove methanol while the lights are off before continuing the conversion with the lights on. A photocatalytic model is being developed to increase our understanding of the operation and optimization of our photocatalytic reactor system.

The explorations of adding alkali-metal ions including Li+, Na+, K+, and Rb+ to modify our silica-supported metal oxide catalysts are ongoing because alkali-metal ions have electron-donating ability, which leads to an enhancement of basicity of metal oxides. These investigations will be helpful in understanding the effect of an alkali-metal addition for partial oxidation of light alkanes. Furthermore, the addition of NO to increase the conversion and selectivity has been investigated.

Expected Results:

Worldwide reserves of methane are an underutilized resource. For example, substantial quantities of methane are usually associated with the extraction of crude oil. Methane is usually flared into the atmosphere because it is too expensive to transport for industrial and commercial use. The production of methanol from methane provides many economic and pollution-prevention dividends.

It is expected that the use of methanol will reduce reduce greenhouse gases associated with the extraction of crude oil. Methanol is in demand as an inexpensive fuel oxygenate and a feed stock for commodity chemicals. It is being investigated as an alternative fuel for conventional auto engines, which will reduce CO, NOx, volatile organics, and benzene emissions from automobiles making it a cleaner burning fuel than coal or petroleum.

Publications and Presentations:

Publications have been submitted on this subproject: View all 2 publications for this subprojectView all 157 publications for this center

Supplemental Keywords:

technology for sustainable environment, environmental chemistry, clean technology, environmental engineering, pollution prevention, cleaner production, catalytic research, semiconductors, photocatalytic reactor, methanol, alternative fuels, greenhouse gases, global climate change, motor vehicle emissions, benzene., RFA, Scientific Discipline, Air, INTERNATIONAL COOPERATION, TREATMENT/CONTROL, Ecosystem Protection/Environmental Exposure & Risk, Sustainable Industry/Business, Chemical Engineering, cleaner production/pollution prevention, Environmental Chemistry, Sustainable Environment, Chemistry, climate change, Air Pollution Effects, Technology, Technology for Sustainable Environment, computing technology, Engineering, pollution prevention, Environmental Engineering, Atmosphere, environmental monitoring, cleaner production, clean technologies, motor vehicle emissions, pollution prevention design tool, data sharing, clean technology, photocatalytic reactor, computer science, modeling, pollution control, catalytic studies, greenhouse gases, computer simulation modeling, environmental simulation and design tools, pollution prevention design, environmental data, alternative fuel, alternative energy source, global warming, Global Climate Change, pollution prevention model, clean manufacturing designs

Progress and Final Reports:

  • 1997
  • Final

  • Main Center Abstract and Reports:

    R825370    EERC - National Center for Clean Industrial and Treatment Technologies (CenCITT)

    Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
    R825370C032 Means for Producing an Entirely New Generation of Lignin-Based Plastics
    R825370C042 Environmentally Conscious Design for Construction
    R825370C046 Clean Process Advisory System (CPAS) Core Activities
    R825370C048 Investigation of the Partial Oxidation of Methane to Methanol in a Simulated Countercurrent Moving Bed Reactor
    R825370C054 Predictive Tool for Ultrafiltration Performance
    R825370C055 Heuristic Reactor Design for Clean Synthesis and Processing - Separative Reactors
    R825370C056 Characterization of Selective Solid Acid Catalysts Towards the Rational Design of Catalytic Reactions
    R825370C057 Environmentally Conscious Manufacturing: Prediction of Processing Waste Streams for Discrete Products
    R825370C064 The Physical Properties Management System (PPMS™): A P2 Engineering Aid to Support Process Design and Analysis
    R825370C065 Development and Testing of Pollution Prevention Design Aids for Process Analysis and Decision Making
    R825370C066 Design Tools for Chemical Process Safety: Accident Probability
    R825370C067 Environmentally Conscious Manufacturing: Design for Disassembly (DFD) in De-Manufacturing of Products
    R825370C068 An Economic Comparison of Wet and Dry Machining
    R825370C069 In-Line Copper Recovery Technology
    R825370C070 Selective Catalytic Hydrogenation of Lactic Acid
    R825370C071 Biosynthesis of Polyhydroxyalkanoate Polymers from Industrial Wastewater
    R825370C072 Tin Zeolites for Partial Oxidation Catalysis
    R825370C073 Development of a High Performance Photocatalytic Reactor System for the Production of Methanol from Methane in the Gas Phase
    R825370C074 Recovery of Waste Polymer Generated by Lost Foam Technology in the Metal Casting Industry
    R825370C075 Industrial Implementation of the P2 Framework
    R825370C076 Establishing Automated Linkages Between Existing P2-Related Software Design Tools
    R825370C077 Integrated Applications of the Clean Process Advisory System to P2-Conscious Process Analysis and Improvement
    R825370C078 Development of Environmental Indices for Green Chemical Production and Use