Potential Applications of Zeolite Membranes in Reaction Coupling Separation Processes
Abstract
:1. Introduction
1.1. Process Intensification, Membranes and Membrane Reactors
- adsorption of the molecule onto the interface of the high-pressure side of the membrane;
- dissolution of the molecule into the membrane at the interface and diffusion of the molecule through;
- the elution of the molecule from the membrane at the interface;
- desorption of the molecule from the low pressure side of the membrane.
Membrane system | Reaction | Reference |
---|---|---|
Pd-Alloy membrane reactor | Dehydrogenation of hydrocarbons | [6] |
Pd-Rh foil membrane | Dehydrogenation of cyclohexanediol to pyrocatechol | [7] |
Pd-Ru-Ni Alloy membrane | Dehydrogenation of isopropanol | [8] |
Pt/Al2O3-Pd membrane | Dehydrogenation of cyclohexane to benzene | [9] |
Ceramic membranes | Polymeric membranes |
---|---|
Do not swell | Do swell |
Possibility of uniform, molecular sized pores allowing for molecular sieving | Do not have uniform molecular sized pores |
Chemically resistant to solvents and low pH | Not chemically stable. Denatured at low pH |
Thermally stable | Not thermally stable, denatured at high temperature |
High cost of production | Lower cost of production |
More brittle | Less brittle |
1.2. Zeolite, Zeolite Membranes and Zeolite Membrane Reactors
1.2.1. Zeolites
1.2.2. Zeolite Membranes
Synthesis technique | Description | Reference |
---|---|---|
Liquid-phase hydrothermal (LH) synthesis technique (in situ hydrothermal synthesis) (LH) | One-step deposition of a layer containing the Si and Al precursor as a dry amorphous aluminosilicate gel onto a support using sol-gel technique followed by zeolitization under vapor | [75,76,77] |
Vapor phase transport (VPT) technique | Two-step technique involving coating a support with amorphous gel containing Si and Al , followed by crystallization | [70,71] |
Secondary seeded growth (SSG) technique | Two-step technique involving initial ex-situ seeding of a support by previously synthesized zeolite crystals followed by hydrothermal crystallization | [78,79,80,81,82] |
Pore-plugging hydrothermal (PH) synthesis technique | One-stage technique involving growing zeolite crystals within pores of a support until the pores are completely blocked the zeolite materials | [53,54,55,66,67,68] |
- Elimination of seeding technique because the zeolite crystals embedded within the matrix of polymer-zeolite composite, used as supports, serve as seeds;
- Easy formation of uniform crystal distribution, enhancing reproducibility;
- Possibility of obtaining membranes at low temperatures, reducing energy cost;
- Desirable mechanical properties, economical processability of the polymers;
- Unique structure of the dispersed inorganic phase possesses unique structure, good surface chemistry and mechanical strength.
1.2.3. Zeolite Membrane Reactors
- Mole balance in the catalytic bed : Material in – Material out + Generation = Accumulation.
- Rate law that accounts for disappearance of reactant: . Where , the reaction rate; , reaction rate constant; , reactant concentration and , the reaction order.
- Transport law accounting for the transport or flux of product through the membrane: . Where , is the flux of the product through the membrane; , the mass transfer coefficient; and , the concentration gradient across the membrane. It is noteworthy to mention that the transport law takes into account the adsorption-diffusion mechanism that governs the transport of molecule through zeolite membranes.
2. Potential Applications of Zeolite Membrane Reactors in Reactive-Separation
2.1. Synthesis of Chemicals in the Chemical and Petrochemical Industry
- Presence of cheap and high quality membrane supports. In some cases, cheap supports are modified before synthesis or membrane defects healed for enhanced membrane selectivities.
- Optimized membrane synthesis conditions and membrane configuration that could result in very reasonable membrane fluxes. In this regard, the use of a hollow fiber membrane configuration is a promising option [56].
2.2. Potential Applications in the Fuel Cell System
2.3. Application in Selective Removal of Water from Industrial Processes
Process | Reaction | Reference |
---|---|---|
Production of N-Methylpyrrolidone (NMP) from γ-butyrolactone | [122,123] | |
Tetrahydrofuran from 1,4-butanediol | [124,125,126] | |
Conversion of methanol to a mixture of hydrocarbons in the Mobil process | [127] | |
Dioctylphthalate, (DOP), from phthalic anhydride and 2-ethylhexanol | [128] | |
Glyoxal from ethyleneglycol | [129,130,131,132,133] | |
1,4-Dioxane from diglycol | [134,135] | |
Morpholine from diethanolamine | [136,137,138] | |
Ethylene diamine from monoethanol amine | [139,140,141,142] | |
Esters of ethylene glycol monoalkyl ethers | [143] | |
2-Vinyl picoline from 2-picoline | [144] | |
2- and 4-Picoline from acetaldehyde and ammonia | [145] | |
Anthraquinone from anthracene | [146,147] | |
Benzoic acid from toluene | [148,149] | |
Butene oxidation to maleic anhydride | [150,151,152] | |
Sorbitans (monolaurate, monopalmitate, monostearate, etc.) from D- sorbitol and fatty acids | [153,154,155] |
2.4. Application in Water Treatment and Purification Industry
2.5. Application in the Bio-Refinery Industry
3. Conclusions and Future Outlook
- Zeolite membrane synthesis and optimization. Reaction coupling separation using ZCMRs requires highly-selective and defect- free zeolite membrane prepared through a robust and scalable reproducible technique. Also the zeolite membranes should display reasonable membrane flux for commercialization. However to enhance separation and catalytic performance of ZCMRs, factors like geometry and operational conditions, have to be optimized. Recently, further advances in catalytic membrane reactors and reactions have resulted in development of selective zeolite membranes with hollow fiber configurations. These membrane configurations offer great advantages as the hollow structure can be packed with catalysts for catalytic processes with separation occurring simultaneously [183]. In comparison with conventional membranes, hollow fibers have a larger surface area-to-volume ratios >3000 m2/m3 and a thinner membrane wall, resulting in about 30% increase in membrane flux , when compared with membrane tubes fabricated using the same synthesis technique [56]. In addition, several hollow fibers can be made into fiber bundles, thereby reducing both the size and cost of the permeating modules for selective water removal from industrial processes. Therefore, improvement is required in this line to make the incorporation of the catalytic centre into the membranes possible without unnecessarily increasing the thickness of the inorganic supports, promoting permeability without forming pinholes or cracks. At the same time, limitations in terms of uniform temperature control and heat transfer may be overcome.
- Zeolite membrane reactor configuration and reactor analysis. To avoid formation of undesired products in IZCMRs and thus enhance the yield, conversion and overall reactor performance, the reaction rate to membrane flux ratio should approach one. For example in PX isomerization, if the reaction rate > membrane flux (in the case of packed-bed ZCMRs), PX is isomerized to undesirable products like o-xylene and m-xylene. On the other hand, if the membrane flux > reaction rate, isomerization of m-xylene to p-xylene is affected. Therefore a suitable reactor configuration is essential to strike a balance between membrane performance and catalyst performance. In general terms, ZCMRs could be about 10 times more active than IZCMRs provided that the membrane thickness and porous texture, as well as the quantity and location of the catalyst in the membranes are adapted to the reaction kinetics [120,121]. Research efforts are still limited in the development and application of ZCMRs due to challenges in ensuring homogenous distribution of catalytic particles/layer on the membranes.
- Zeolite membrane and zeolite membrane stability. Although zeolite membranes and zeolite membrane reactors can be employed at high temperature and chemically harsh conditions, their long-term thermal stability and operational stability under real operating conditions require significant improvement to attract industrial acceptance. Most of the fabricated zeolite membranes are thermally stable up to 400–500 oC. However, some industrial applications occur at higher temperatures, requiring high thermally stable membranes. Efforts are required to produce such membranes to extend future applications of ZCMRs.
- Techno-economical feasibility and scale-up studies. Techno-economical feasibility studies of ZCMRs are essential. The studies will lucidly elucidate the comparative advantages of the technology over existing conventional technologies. Virtually, all research efforts reported on the development and application of ZCMRs are still limited to laboratory scale studies. In view of this, scale-up studies of the technology are necessary to evaluate the competitiveness of the technology with existing processes to fast-track commercialization of the technology.
Supplementary Files
Supplementary File 1References
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Daramola, M.O.; Aransiola, E.F.; Ojumu, T.V. Potential Applications of Zeolite Membranes in Reaction Coupling Separation Processes. Materials 2012, 5, 2101-2136. https://doi.org/10.3390/ma5112101
Daramola MO, Aransiola EF, Ojumu TV. Potential Applications of Zeolite Membranes in Reaction Coupling Separation Processes. Materials. 2012; 5(11):2101-2136. https://doi.org/10.3390/ma5112101
Chicago/Turabian StyleDaramola, Michael O., Elizabeth F. Aransiola, and Tunde V. Ojumu. 2012. "Potential Applications of Zeolite Membranes in Reaction Coupling Separation Processes" Materials 5, no. 11: 2101-2136. https://doi.org/10.3390/ma5112101