Technology Type
- Type
- Propylene Oxide via the Organic Peroxide Method
- Process
- Oxidation
- Abbreviation
- Description
-
Process Summary
The organic peroxide method, also known as the hydroperoxide method, is a widely used industrial process for producing propylene oxide (PO). This method was first developed in the 1970s by Halcon Corp. and Atlantic Richfield Oil Corp. (ARCO). It involves the indirect epoxidation of propylene using organic peroxides such as ethylbenzene hydroperoxide (EBHP) or tert-butyl hydroperoxide (TBHP). The process co-produces valuable by-products: styrene monomer (SM) in the SMPO process or tert-butanol (TBA) in the TBA process.
SMPO Process (PO/SM Method)
The SMPO process uses ethylbenzene as a feedstock to produce PO and SM.
The key steps are as follows:
1. Ethylbenzene Epoxidation
- Ethylbenzene is oxidized with air to produce ethylbenzene hydroperoxide (EBHP).
- Catalysts: Molybdenum-based homogeneous catalysts or titanium-silica-supported heterogeneous catalysts are used to enhance selectivity.
2. Epoxidation
- EBHP reacts with propylene in an epoxidation reactor, producing PO and o-methylbenzyl alcohol as intermediates.
3. Dehydration
-
o-Methylbenzyl alcohol undergoes dehydration in the presence of an acid catalyst to form styrene monomer (SM).
Co-Product Ratio
-
Approximately 2.5 tons of SM are co-produced for every ton of PO.
TBA Prodcess (PO/TBA Method)
The TBA process uses isobutane as a feedstock to produce PO and TBA.
The key steps are as follows:
1. Isobutane Epoxidation
- Isobutane is oxidized with air to form tert-butyl hydroperoxide (TBHP).
2. Oxidation
- TBHP reacts with propylene in an epoxidation reactor, producing PO and TBA as co-products.
3. TBA Utilization
- TBA can be dehydrated to form isobutylene.
- Isobutylene can be further reacted with methanol to produce methyl tertiary-butyl ether (MTBE), a gasoline additive.
Co-Product Ratio
-
Approximately 2.1 tons of TBA-derived products are co-produced for every ton of PO.
Comparison of SMPO and TBA Methods
Feature SMPO Method TBA Method Feedstock Ethylbenzene Isobutane Organic Peroxide Ethylbenzene Hydroperoxide (EBHP) Tert-Butyl Hydroperoxide (TBHP) Co-Product Styrene Monomer (SM) Tert-Butanol (TBA) Co-Product Ratio 2.5 tons SM per ton PO 2.1 tons TBA per ton PO Application of Co-Product Plastics, rubber manufacturing MTBE production, gasoline additive Environmental Impact No chlorine required No chlorine required Economic Sensitivity Dependent on styrene market demand Dependent on MTBE market demand Market Considerations
Both methods are efficient and environmentally friendly but face challenges due to market dependencies:
-
The SMPO method relies on strong demand for styrene monomer, primarily used in plastics like polystyrene and ABS resins.
-
The TBA method depends on demand for fuel additives like MTBE, which has declined in some regions due to environmental regulations.
As a result, newer technologies like HPPO (Hydrogen Peroxide Propylene Oxide) are gaining traction due to their single-product focus and reduced reliance on co-product markets.
References
- Tomonori KAWABATA et al., Trends and Views in the Development of Technologies for Propylene Oxide Production, R&D Report SUMITOMO KAGAKU, vol. 2019.
- Junpei T SUJI et al., Development of New Propylene Oxide Process, R&D Report SUMITOMO KAGAKU, vol. 2006-I.
- SULE KALYONCU, Sep 2012, Catalytic Reaction of Propylene to Propylene Oxide on various Catalysts, Middle Est Technical University.
- Link
System Info
- Updated by
-
Kokel, Nicolas
- Updated
- 3/13/2025 3:50 PM
- Added
- 3/13/2025 1:05 PM

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