Homogeneous catalytic hydroformylation of propylene in propane-expanded solvent media

Liu, Dupeng; Chaudhari, Raghunath V.; Subramaniam, Bala

doi:10.1016/j.ces.2018.04.071

Cited by 10 publications

(10 citation statements)

References 21 publications

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“…The annual butyraldehyde capacity for the plant scale simulations was set at 300000 tons/year at a 0.9 on-stream factor (i.e., 328 on-stream days). The data for simulating the CATOFIN PDH and conventional PHF process were obtained from literature and patents. , The data for simulating the PXL process were obtained from laboratory-scale experiments. , To simplify the process for better convergence, the mass and energy balances for PDH catalyst regeneration were calculated separately. The operating parameters are summarized in Table .…”

Section: Methodsmentioning

confidence: 99%

“…Recently, we demonstrated that refinery-grade propane/propylene mixtures can be used directly for propylene hydroformylation without the need for purification to obtain polymer-grade propylene. , The mixed propylene/propane feed also provides reaction benefits by volumetrically expanding the reaction mixture to yield gas-expanded liquids (GXLs) with tunable physicochemical properties. Unlike conventional reaction media, the H 2 /CO ratio in GXL media can be enhanced by simply increasing the partial pressure of propane. , For rhodium/triphenylphosphine catalyzed propylene hydroformylation performed between 70 and 100 °C and pressures up to 2.0 MPa, the n/i aldehyde ratio is increased by up to 45% in propane-expanded liquids (PXLs) . Given that the refinery-grade propylene feedstock (55% propylene + 45% propane) costs up to 50% less than polymer-grade propylene, the PXL-based hydroformylation process has potential energy savings and economic/environmental benefits …”

Section: Introductionmentioning

confidence: 99%

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Enriching Propane/Propylene Mixture by Selective Propylene Hydroformylation: Economic and Environmental Impact Analyses

Liu

Chaudhari

Subramaniam

2020

ACS Sustainable Chem. Eng.

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Industrial propylene hydroformylation (PHF) processes use polymer-grade propylene (99.99 wt% propylene) obtained from the energy-intensive distillation of propylene/ propane mixtures produced in propane dehydrogenation (PDH) reactors. The typical effluent from a PDH reactor consists of 55% propylene and 45% propane, referred to as refinery-grade propylene. Recently, it was shown that refinery-grade propylene (60−70% purity, the rest is propane) can be directly used for propylene hydroformylation over Rh-based complexes as catalysts without the need for C 3 distillation. The enriched propane is recycled back to the PDH reactor. At typical industrial conditions (2.5 MPa, 90 °C), hydroformylation with refinery-grade propylene occurs in a propane-expanded liquid (PXL) phase. In the PXL phase, the syngas solubility can be easily tuned with pressure to enhance activity and product selectivity. Comparative economic analyses show >20% savings in capital investment for the PXL process compared to the conventional process. Elimination of the energy-intensive C 3 distillation step also reduces the PXL process utility cost by approximately 20% compared to that of the conventional process. The overall savings in total production cost for the PXL process is approximately 9% or 9 cents/lb product, which translates into an annual savings of nearly $12 M for a 300 kt/y plant. Comparative gate-to-gate environmental impact analyses by the economic input−output life cycle assessment (EIO-LCA) method shows that the lower material and energy consumption in the PXL process results in reduced environmental impacts (approximately 20% reduction in each of the following categories: greenhouse gas emission, air pollutants and toxics release) than the conventional process. These results indicate that the PXL process is a greener and more sustainable process for butyraldehyde production.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Enriching Propane/Propylene Mixture by Selective Propylene Hydroformylation: Economic and Environmental Impact Analyses

Liu

Chaudhari

Subramaniam

2020

ACS Sustainable Chem. Eng.

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“…Later, Smith and co-workers reported another Rh-catalyzed protocol and furthered the selectivity to 74% for adipaldehyde, which can be oxidized to adipic acid using oxone . Liu and co-workers reported cost-effective hydroformylation processes, which show significant environmental and economic promises for industrial implementation. − Overall, the protocol of the butadiene route offers a nitric-acid free route to access adipic acid, but its yield and efficiency requires significant improvement compared to the convention cyclohexane route. Obviously, there is a strong need to develop alternative oxidants for this process.…”

Section: Introductionmentioning

confidence: 99%

Chemical Synthesis of Adipic Acid from Glucose and Derivatives: Challenges for Nanocatalyst Design

Jin

Liu

Zhang

et al. 2020

ACS Sustainable Chem. Eng.

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Adipic acid is an essential building block for the nylon industry, but its production continues to rely on fossil-derived benzene and generates a substantial amount of N 2 O every year. Recognizing the environmental impact of conventional adipic acid production and motivated by societal interests toward a sustainable future, the production of adipic acid should switch toward a renewable feedstock and proceed with a nitric acid-free protocol. In light of this transition, glucose emerges as a suitable feedstock to replace benzene for bioadipic acid production. It can be chemically converted into bioadipic acid via two different routes, forming either glucaric acid or 2,5-furandicarboxylic acid as the respective key intermediates. However, these transformations are challenged by various issues, such as retro-aldol condensation, which fragments glucose into smaller organic byproducts, and catalyst instability, which compromises the reaction rates. This perspective addresses the potentials and challenges in nanocatalyst design and discusses how catalyst morphology tailoring and metal−support interaction tuning can be revised systematically to maximize the yield of bioadipic acid. The influence of catalyst structures on selective activation of C−H (oxidation) and C−O bond (hydrogenolysis) of the intermediates is critically discussed. The electronic features of bimetallic and metal−acid/base hybridized catalysts on C−H and C−O bond activation have been correlated in this work. The goal of this perspective aims to provide insights on novel nanocatalysts designed to improve bioadipic acid production from sustainable feedstocks.

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“…The chemistry of carbon monoxide is one of the main directions in the production of liquid transportation fuels and valuable chemicals. Fischer-Tropsch synthesis, methanol synthesis, hydroformylation, and carbonylation are the major reactions used for these purposes [1][2][3][4][5][6]. In C 1 chemistry, synthesis gas plays the role of the reactant and also can be the part of the active catalyst complex [7,8].…”

Section: Introductionmentioning

confidence: 99%

Synthesis‐Gas Absorption under Real Process Conditions: Thermodynamic Aspects

et al. 2019

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The solubility of synthesis gas was measured in the temperature range of 100–300 °C and pressure range of 1.0–5.0 MPa in polar (2‐propanol) and nonpolar (n‐dodecane) solvents. Thermodynamic parameters of the absorption, such as the Henry constant, absorption enthalpy, and apparent activation energy of absorption, were calculated on the basis of the obtained results. The phase equilibrium was calculated by using the Soave‐Redlich‐Kwong cubic equation of state, which could be used to predict the optimal process conditions for liquid‐phase Fischer‐Tropsch reactions in different solvents.

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Homogeneous catalytic hydroformylation of propylene in propane-expanded solvent media

Cited by 10 publications

References 21 publications

Enriching Propane/Propylene Mixture by Selective Propylene Hydroformylation: Economic and Environmental Impact Analyses

Enriching Propane/Propylene Mixture by Selective Propylene Hydroformylation: Economic and Environmental Impact Analyses

Chemical Synthesis of Adipic Acid from Glucose and Derivatives: Challenges for Nanocatalyst Design

Synthesis‐Gas Absorption under Real Process Conditions: Thermodynamic Aspects

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