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Auto-Tandem Catalytic Reductive Hydroformylation in a CO2-Switchable Solvent System
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ACS Sustainable Chemistry & Engineering

Cite this: ACS Sustainable Chem. Eng. 2022, 10, 11, 3749–3756
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https://doi.org/10.1021/acssuschemeng.2c00419
Published March 8, 2022

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Abstract

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Upgradation of olefin-enriched Fischer–Tropsch cuts by the synthesis of alcohols leads to drop-in-capable biosynthetic fuels with low carbon emissions. As an alternative to the conventional two-step production of long-chain alcohols, tandem catalytic systems improve the energy and resource efficiency. Herein, we present an auto-tandem catalytic system for the production of alcohols from olefin–paraffin mixtures. By utilization of a tertiary alkanolamine as the ligand as well as the switchable component in the solvent system, a lean reaction system capable of catalyst recycling was developed. The system was characterized with regard to the switchable solvent separation approach and reaction parameters, resulting in alcohol yields of up to 99.5% and turnover frequencies of up to 764 h–1. By recycling the catalyst in 10 consecutive reactions, a total turnover number of 2810 was achieved.

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Synopsis

Double utilization of alkanolamines: As nonphosphine ligand for tandem catalysis and for switching the phase behavior for product separation

Introduction

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As an immediate measure to reduce carbon dioxide emissions of road transport, biosynthetic fuels enable the ongoing use of existing infrastructure and vehicles. (1−3) One pathway toward renewable fuels is olefin-selective Fischer–Tropsch (FT) synthesis with bio-syngas. (4) The FT-derived olefins allow for subsequent upgrading of such fuels and enable tailor-made fuel properties. Potential additives to biosynthetic fuels are alcohols, which are able to reduce emissions and improve combustion characteristics while aiding to achieve drop-in capability. (5−7)
Alcohols in the C6–C11 range (for diesel requirements) are industrially produced in multistep processes, predominantly in hydroformylation–hydrogenation reactions with isolated aldehyde intermediates. (8,9) Aldehydes represent platform chemicals in industry and lead to various products, including carboxylic acids, amines, and alcohols. For fuel production, direct production of alcohols without intermediate steps could increase the resource efficiency. (10,11)
Direct conversion of olefins to alcohols is known as “reductive hydroformylation”, an example of tandem catalysis and the combination of a hydroformylation and a hydrogenation step. Several tandem catalytic systems for this conversion have been investigated: separate catalysts (orthogonal tandem catalysis) for either reaction step (12,13) and so-called “assisted tandem catalysis” in which both steps are conducted with the same catalyst, although under different reaction conditions. (14) However, auto-tandem catalysis─using the same catalyst for both reaction steps under the same conditions─represents the most efficient variant. (11) Auto-tandem reductive hydroformylation was first described for cobalt-based catalysts, although they achieve poor selectivity and require harsh conditions. (15,16) Recent investigations usually focus on rhodium catalysts due to their superior activity in hydroformylation, which are capable of auto-tandem reductive hydroformylation, e.g., in combination with tertiary alkylamines. (17−24) Necessary steric and electronic properties of amines in reductive hydroformylation were previously published by our group. (21,25)
However, most existing tandem catalytic systems for this reaction inherit the most fundamental challenge in homogeneous catalysis: difficult recovery of the expensive catalyst(s). A rather unconventional approach to catalyst recycling is the so-called “switchable solvent system”. (26) In this system, the addition of a trigger (commonly CO2) to a switchable component changes its ionic strength and therefore the phase behavior of the mixture. (27)
Figure 1 shows the process concept of the switchable phase behavior with the addition of CO2 to an amine. However, the reaction is carried out under monophasic conditions (Figure 1, left) and product separation is achieved by the addition of CO2, which causes the mixture to separate into two liquid phases (Figure 1, right).

Figure 1

Figure 1. General concept of the CO2-switchable phase behavior.

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This effect eliminates the necessity of additional solvents for extraction and their respective energy-intensive recovery and further increases the efficiency of a tandem catalytic system. (27−29) In this manuscript, we present a water/alkanolamine-based CO2-switchable solvent system for reductive hydroformylation to yield alcohols from olefins in one step.
The alkanolamine serves two functions in this system: it is part of the catalyst system (ligand) and also serves as a switchable component (solvent) to influence the phase behavior of the reaction mixture. Given the polar nature of the catalyst (ionic rhodium complexes and a polar amine), the catalyst accumulates in the lower (polar) phase, and the nonpolar reaction products accumulate in the upper (organic) phase. Hence, this technique enables the recovery of the catalyst.

Results and Discussion

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Scheme 1 shows the reductive hydroformylation reaction network. As a representation of FT cuts, an olefin–paraffin mixture was used as the model substrate, consisting of 1-octene and n-heptane (1:1 mass ratio). The olefins react to either linear (1a) or branched (2a) aldehydes in the first reaction step. Possible side reactions are the formation of internal, isomerized olefins (3) as well as hydrogenation of the olefins to the corresponding paraffin (4); however, in all experiments, only traces of paraffins were found, an exceptional selectivity compared to cobalt-based catalyst systems.

Scheme 1

Scheme 1. Reductive Hydroformylation Reaction Network
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Hydroformylation of isomerized olefins (3) leads to further branched aldehydes (5a). In the second reaction step, all intermediate aldehydes (1a + 2a + 5a) are hydrogenated to their corresponding alcohols (1b + 2b + 5b), which represent the desired reaction products. To assess the first reaction step, the combined hydroformylation yield is used (Yhyfo, 1a + 1b + 2a + 2b + 5a + 5b). The total alcohol yield (Yalcohols, 1b + 2b + 5b) is used to evaluate the second reaction step.
The necessary properties of amines in reductive hydroformylation reactions have been determined in previous contributions by our group. Therein, catalytically active species were characterized with operando spectroscopy. Furthermore, the basicity of the amine was determined to be an important parameter; a pKa value of 10 ± 1.5 is necessary for the production of alcohols. (21,25) Also, the steric hindrance of the employed amines needs to be low, and bulky groups on the amines as well as diamines reduced the hydrogenation activity of the system. This disables the control of the regioselectivity of the reactions with bulky ligand systems. However, this is of minor importance for this reaction system; the desired reaction products are primary alcohols as fuel additives, which are not required to be linear.
To avoid reductive amination reactions, (18,30) only tertiary amines are applicable in reductive hydroformylation. Furthermore, the tertiary alkylamines used in previous studies (21) show poor performance in CO2 capture and therefore are not suitable for designing a switchable solvent system.
Instead, alkanolamines are necessary to achieve reasonable “switching power”. (28) Given the aforementioned constraints for amines in reductive hydroformylation, the selection of amines applicable in the reaction as well as separation is rather limited. N,N-Dimethylethanolamine (DMAE) and N,N-diethylethanolamine (DEAE) were identified as suitable polar amine candidates for this reaction.

Investigation of Phase Separation

DMAE led to the undesired formation of solids when pressurized with CO2. On the contrary, when DEAE was used, no formation of solids occurred and hence was used as the switchable component.
To develop a reaction/phase separation system, first the separation step was characterized. In a phase behavior simulation with Aspen Plus (included in the Supporting Information, SI), a water–amine ratio (WAR, mwater/mDEAE) of ≤0.5 was found to be suitable for monophasic behavior during the reaction. These results were validated experimentally by generating potential reaction mixtures with the pure substances present in the reaction (water, DEAE, n-heptane, 1-octene, and n-nonanol). Table 1 summarizes the phase behavior of these simulated reaction mixtures. Since amphiphilic alcohols are produced from nonpolar substrates, the alcohol yield has a large influence on the phase behavior of the reaction mixture.
Table 1. Number of Phases at a Given Surrogate Mixture Compositiona
YalcoholsWAR 0WAR 0.1WAR 0.2WAR 0.3WAR 0.4WAR 0.5
0.00112222
0.25112222
0.50111111
0.75111111
a

Water–amine ratio (WAR, mwater/mDEAE), Yalcohols simulated by replacing 1-octene with n-nonanal.

Generally, low water content of the mixture leads to monophasic behavior for any alcohol yield, i.e., already at the outset of the reaction. With an increased water–amine ratio, these polar components form a separate phase immiscible with the substrate; the initially present two phases merge when a sufficient alcohol concentration is reached.
As a water-less system (WAR = 0) would potentially eliminate any solvent in the reaction system, it would be the most efficient option. Unfortunately, water is necessary for the amine to switch to the ionic form; the reaction network of the protonation of tertiary amines involves carbonate and bicarbonate ions. (31)
Accordingly, no reaction between CO2 and the amine was observed when no water was added to the mixture. Hence, water–amine ratios between 0.1 and 0.5 were considered for further investigations of the phase separation performance (Figure 2).

Figure 2

Figure 2. Product recovery and amine leaching with varying WAR and CO2 loading. Separation conditions: Tsep = 25 °C, tsep = 5 min, product recovery = nalcohol, second phase/nalcohol, total, water–amine ratio (WAR) = mWater/mDEAE, and Y = simulated alcohol yield in the surrogate mixture.

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To investigate the phase behavior and compositions of the formed phases after pressurization with CO2, surrogate mixtures, the previously described mixtures, were pressurized with varying molar ratios between CO2 and DEAE. Figure 2 shows that while the product recovery remains similar for any variation of the parameters, the amount of amine lost into the product phase decreases with higher CO2 loading. This can be attributed to increased ionic strength of the catalyst phase since a higher conversion of DEAE into the protonated form is achieved at high CO2 loading. The loss of amine also decreases slightly with increased water content of the polar phase.

Batch Optimization of Reaction Conditions

The initial reaction conditions for the presented reaction system were adapted from a previously published system developed by our group in which the reaction mixture consisted of acetonitrile as the solvent and diethylmethylamine was used as the amine ligand. (21) These components were replaced by water and N,N-diethylethanolamine, respectively. With the solvent system modified to allow for CO2-switchable behavior, similar activity and alcohol yield were obtained in an initial experiment (Figure 3E, Yalcohols = 70%, compared to 82% in the reference system).

Figure 3

Figure 3. Variation of catalyst concentration. Reaction conditions: n1-octene = 38.4 mmol (6 mL), Vn-heptane = 6 mL, T = 100 °C, tR = 1.5 h, p = 30 bar, CO/H2 = 1:2, φorg = 0.4, Vliq = 30 mL, water–amine ratio = 0.3, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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Given the high catalyst loading necessary for this reaction, one main goal of the investigation was to reduce the required amount of rhodium. At a catalyst concentration of 0.25 mol %, comparable yields were achieved (Figure 3D), leading to a higher turnover number (TONalc, mol alcohols produced per mol of catalyst) of 211 compared to 139 with 0.5 mol %. Further reduction of the catalyst loading led to decreased yield and lower productivity (TONalc) of the catalyst. In particular, the hydrogenation activity of the catalyst system was significantly reduced at lower catalyst loadings (Figure 3A–C). A catalyst concentration of 0.25 mol % has therefore been used for further investigation of this reaction system.
To allow for the desired CO2-switchable behavior of the system, the solvent as well as the amine were replaced with compounds with increased polarity. While this is necessary to separate the nonpolar reaction products from a now polar catalyst phase, the solubility of the nonpolar gaseous substrates as well is expected to be low in this reaction system. (32)
Hence, the influence of the syngas pressure and composition was investigated. A stoichiometric composition (CO/H2 = 1:2 for the tandem reaction) led to higher selectivity toward alcohols compared to a ratio of 1:1 (Figure 4F,I,K).

Figure 4

Figure 4. Variation of Syngas pressure and composition. Reaction conditions: ccat = 0.25 mol %, n1-octene = 38.4 mmol (6 mL), nRh = 0.096 mmol, Vn-heptane = 6 mL, T = 100 °C, tR = 1.5 h, φorg = 0.4, Vliq = 30 mL, water–amine ratio = 0.3, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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Hydrogen excess (CO/H2 = 1:3, Figure 4H) not only leads to similar results with a slightly higher hydrogenation activity but also an increased total pressure. Hence, a ratio of CO/H2 = 1:2 and a total pressure of 60 bar were chosen for the following experiments.
Furthermore, the effect of the reaction temperature was investigated. Lowering the reaction temperature to 60 or 80 °C significantly reduced the activity of the catalyst (Figure 5M,N). Higher reaction temperatures of 120 and 140 °C led to an increased alcohol yield (Figure 5P,Q). Primarily, this can be attributed to the hydroformylation of isooctene (3) to branched aldehydes (5a) and the subsequent production of branched alcohols (5b), which is apparently accelerated at higher temperatures. At 160 °C, isomerized olefins were observed to be the predominant reaction products. At the same time, the catalyst activity for hydrogenation is almost completely abolished. This phenomenon is already visible when increasing the temperature from 120 to 140 °C: the hydrogenation activity decreases and a higher share of aldehyde intermediate remains in the reaction product.

Figure 5

Figure 5. Variation of the reaction temperature. Reaction conditions: ccat = 0.25 mol %, n1-octene = 38.4 mmol (6 mL), nRh = 0.096 mmol, Vn-heptane = 6 mL, p = 60 bar, CO/H2 = 1:2, tR = 1.5 h, φorg = 0.4, Vliq = 30 mL, water–amine ratio = 0.3, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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Most likely, the catalytic species active for hydrogenation are no longer stable at these high temperatures.
Furthermore, the water–amine ratio, important for the phase behavior of the reaction (Table 1), was evaluated using time profile experiments to compare the individual reaction steps. As shown, when characterizing the phase behavior, increased water/amine ratios of ≥0.2 lead to a biphasic start of the reaction and therefore initially cause mass transfer limitations between the two liquid phases. Hence, a reduced initial reaction rate could be expected.
On the contrary, the reaction to alcohols was found to be faster at a water–amine ratio of 0.5 compared to lower ratios (Figure 6I–III). After 90 min, an alcohol yield of 75% was observed. This value increased to 93% after 4 h. Compared to a water–amine ratio of 0.3, less olefin isomers are formed during the first 30 min of the reaction. Potentially, this is due to a lower accessibility of the catalyst for the substrate due to the described mass transfer limitations. Consequently, all following experiments were carried out with a WAR of 0.5.

Figure 6

Figure 6. Time profile experiments with varying water/amine ratios, syngas pressure, and catalyst concentration. Conditions for all graphs: reaction conditions: n1-octene = 166.4 mmol (26 mL), nRh = 0.416 mmol, Vn-heptane = 26 mL, T = 140 °C, CO/H2 = 1:2, φorg = 0.4, Vliq = 130 mL, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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To suppress the formation of internal olefins even further, a pressure increase to 90 bar was investigated. At this pressure, the yield of olefin isomers reached a maximum of only 16% at 30 min (Figure 6IV) compared to 30% at 60 bar (Figure 6III). Furthermore, aldehyde hydrogenation is also accelerated at 90 bar, likely because of an increased concentration of the gaseous substrate in the catalyst phase. The combination of 90 bar and a WAR of 0.5 lead to an overall alcohol yield of 98.4% after 4 h. The initial reaction was also increased, and a turnover frequency (TOFalc) of 422 h–1 was detected in the first 30 min.
The effect of different catalyst concentrations was investigated in time profiles as well (Figure 6V,VI). While the overall reaction rate is the highest at 0.5 mol %, the catalytic productivity (TONalc) is increased at lower catalyst loadings. All investigated catalyst concentrations led to almost quantitative yield after 4 h; hence, the lowest catalyst concentration leads to maximum catalytic productivity. At 0.125 mol %, the highest TONalc (791) as well as the highest initial TOFalc (764 h–1 in the first 30 min) were achieved, which represents the highest catalytic activity for rhodium/amine-catalyzed auto-tandem reductive hydroformylation reported so far. (21,33)

Catalyst Recycling

After investigating the separation and reaction parameters, the gained knowledge was applied in catalyst recycling experiments. The procedure of catalyst recycling in this switchable solvent system is displayed in Figure 7.

Figure 7

Figure 7. Switchable solvent system catalyst recycling concept.

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The system starts as a biphasic mixture (at high water–amine ratios of ≥0.2), which turns into a single phase due to the formation of alcohols (Table 1 and Figure 2). The reaction mixture is then pressurized with CO2 to switch to a liquid–liquid biphasic system. In this generated biphasic mixture, the products accumulate in the upper phase and can be separated by simple decantation. To reuse the catalyst phase in another reaction run, CO2 must be removed from the amine to restore the initial reaction conditions for the next cycle.
In a first proof-of-concept experiment (Figure 8) for the described recycling approach, the slow release of CO2 from DEAE at standard conditions and the air stability of tertiary amines were utilized to conduct the phase separation outside of the reactor in a separatory funnel. As this experiment was carried out using 0.25 mol % of the catalyst, the achieved total turnover number of 773 corresponds to an approximate twofold increase of catalytic productivity; the maximum TONalc achievable in a single batch reaction would be 400. This proves the feasibility of the catalyst recycling concept. However, the alcohol yield drops after each run, suggesting the presence of catalyst leaching or deactivation.

Figure 8

Figure 8. Proof-of-concept recycling experiment. Reaction conditions: ccat = 0.25 mol %, n1-octene = 166.4 mmol (26 mL), nRh = 0.416 mmol, Vn-heptane = 26 mL, T = 140 °C, p = 90 bar, CO/H2 = 1:2, tR = 1.5 h, φorg = 0.4, Vliq = 130 mL, water–amine ratio = 0.5, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2]; separation conditions: Tsep = 25 °C, tsep = 5 min, nCO2/nDEAE = 2.0, Trev = 70 °C, and trev = 20 min.

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Hence, inductively coupled plasma mass spectrometry (ICP-MS) measurements were conducted to quantify the rhodium concentration in the organic product phase. In the first four runs, a rhodium leaching of 5–15 ppm was detected. However, in the fifth run, catalyst leaching increased to 53 ppm (5.2% of 8.1% in total); at the same time, a strong decrease of catalyst activity was observed. This leads to the assumption that nonpolar catalyst species were formed, which are especially less active for aldehyde hydrogenation. Potentially, this was caused either by repeated air contact during the separation or the absence of a CO2 atmosphere during the actual phase separation. Hence, for the following experiments, a more sophisticated reaction setup allowing the separation under CO2 pressure was used. The setup is further described in the Supporting Information.
To increase the ionic strength of the catalyst phase and to induce phase separation, DEAE is converted into a protonated compound. Likely, this protonated species is incapable of stabilizing the ionic rhodium species, reported as the active catalyst during previous investigations. (21,34,35) Virtually removing the amine from the reaction mixture to switch the phase behavior could explain the deactivation of the catalyst in this experiment.
To circumvent this phenomenon, a recycling experiment with a deficiency of CO2 compared to the amine (nCO2/nDEAE = 0.9) was conducted. This leads to the presence of nonprotonated DEAE during phase separation, which should stabilize the catalyst. Figure 9 indicates that this approach improves the stability of the catalyst. Compared to the experiment in Figure 8, this recycling experiment resulted in stable catalytic activity over at least three reaction runs. From reaction run 4 onward, low aldehyde hydrogenation activity is observable, which causes an increased share of the intermediate in the reaction product. In total, a TTONalc of 2810 for the auto-tandem production of alcohols was achieved in this experiment.

Figure 9

Figure 9. Recycling experiment with reduced CO2 loading in phase separation. Reaction conditions: ccat = 0.25 mol %, n1-octene = 166.4 mmol (26 mL), nRh = 0.416 mmol, Vn-heptane = 26 mL, T = 140 °C, p = 90 bar, CO/H2 = 1:2, tR = 3 h, φorg = 0.4, Vliq = 50 mL, water–amine ratio = 0.5, n = 2000 min–1, and catalyst = [Rh(acac)(CO)2]; separation conditions: Tsep = 25 °C, tsep = 5 min, nCO2/nDEAE = 0.9, Trev = 70 °C, and trev = 20 min.

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However, as already observed in the phase separation experiments (Figure 2), increased amine loss into the organic phase follows from the reduced ratio between CO2 and amine. Hence, a makeup of amine is required and was performed in this experiment. This loss of amine furthermore is an explanation for the increased catalyst leaching observed in this experiment. Interestingly, more catalyst is lost during this experiment (37% in total), but the activity of the catalyst was maintained for a longer period of time. This suggests the presence of an additional deactivation mechanism linked to the CO2-induced phase switching, leading to a tradeoff between the activity of the catalyst and the efficiency of the recycling concept. This effect should be further characterized using operando spectroscopy in future investigations.

Conclusions

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In this work, a switchable solvent approach for reductive hydroformylation was investigated in batch and recycling experiments. The use of N,N-diethylaminoethanol as the switchable component as well as the catalyst ligand and water as the only additional solvent led to a lean system for auto-tandem reductive hydroformylation. By characterizing the main influence parameters, the switchable solvent approach for catalyst recycling was proven to be feasible. The system showed a strong dependency on the water–amine ratio present in the reaction as well as the CO2–amine ratio applied during phase separation. After optimization in batch experiments, the reaction system achieved alcohol yields of up to 99%. Furthermore, a maximum turnover number of 791 in a single batch reaction was detected and an initial turnover frequency of 764 h–1 (during the first 30 min) was achieved. To the best of our knowledge, this is the most active rhodium-based auto-tandem system for reductive hydroformylation reported so far. After investigation of the reaction and separation technique regarding catalytic stability, recycling the catalyst nine times was possible. The utilization of the catalyst was improved, achieving a TTONalc of 2810 for tandem catalytic alcohol production. Further improvement of the catalytic stability is accessible by investigations using operando spectroscopy. Advanced process control of the separation conditions in an improved reaction setup could potentially reduce the loss of amine and therefore reduce catalyst loss and deactivation.

Supporting Information

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c00419.

  • Detailed experimental protocol and information on the used equipment, additional information on the phase behavior simulation, and IR spectra of CO2 loaded and regenerated reaction mixture (PDF)

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Author Information

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  • Corresponding Author
  • Authors
    • Sebastian Püschel - Max Planck Institute for Chemical Energy Conversion, 45470 Mülheim an der Ruhr, Germany
    • Jan Sadowski - Max Planck Institute for Chemical Energy Conversion, 45470 Mülheim an der Ruhr, Germany
    • Thorsten Rösler - Max Planck Institute for Chemical Energy Conversion, 45470 Mülheim an der Ruhr, Germany
    • Kira Ruth Ehmann - Max Planck Institute for Chemical Energy Conversion, 45470 Mülheim an der Ruhr, Germany;  Orcidhttps://orcid.org/0000-0003-2412-4406
    • Walter Leitner - Max Planck Institute for Chemical Energy Conversion, 45470 Mülheim an der Ruhr, Germany;  Institute for Technical and Macromolecular Chemistry, RWTH Aachen University, 52074 Aachen, Germany;  Orcidhttps://orcid.org/0000-0001-6100-9656
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    The project Robust and Efficient processes and technologies for Drop In renewable FUELs for road transport (REDIFUEL) has received funding from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No. 817612. Open access funded by Max Planck Society.

  • Notes
    The authors declare no competing financial interest.

References

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    The use of modern biofuels in mobile applications has an enormous potential to reduce greenhouse gases as well as engine pollutant emissions, such as soot or nitrogen oxides. This beneficial effect is directly related to the mol. structure of the biofuel as a product of an optimized prodn. process. To understand the influence and emission redn. potential of the large variety of different fuel properties, this study aims to identify desirable fuel characteristics and define optimized biofuel components. In a first step, a literature survey is carried out, focusing on the impact of the cetane no., boiling characteristics, and arom. and oxygen contents on the diesel combustion process. The incorporated investigations that analyze the combustion behavior, engine efficiency, and emission performance underline the potential of tailoring fuels to desired properties. From this foundation, a model-based anal. of desired fuel properties was conducted, using a large database with 32 different fuels (single mols. and fuel mixts.). With multiple correlation methods, different fuel properties can be used to predict the emission performance of the engine. The following fuel optimization based on emission performance and engine efficiency results in ideal fuel properties for diesel engine combustion. As it turns out, a blend of 2-methyltetrahydrofurane (2-MTHF) (which can be derived from cellulose) blended with di-n-butylether complies with the desired fuel properties, which were defined before. In combination with an improved homogeneous low-temp. combustion process and an increased ignition delay, a nearly soot-free diesel combustion over a wide load range is realized. The oxygenated fuel enables increased exhaust gas recirculation (EGR) rates while maintaining the high engine efficiency of the diesel process.
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    Jeske, K.; Kizilkaya, A. C.; López-Luque, I.; Pfänder, N.; Bartsch, M.; Concepción, P.; Prieto, G. Design of Cobalt Fischer–Tropsch Catalysts for the Combined Production of Liquid Fuels and Olefin Chemicals from Hydrogen-Rich Syngas. ACS Catal. 2021, 11, 4784– 4798,  DOI: 10.1021/acscatal.0c05027
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    Design of Cobalt Fischer-Tropsch Catalysts for the Combined Production of Liquid Fuels and Olefin Chemicals from Hydrogen-Rich Syngas
    Jeske, Kai; Kizilkaya, Ali Can; Lopez-Luque, Ivan; Pfaender, Norbert; Bartsch, Mathias; Concepcion, Patricia; Prieto, Gonzalo
    ACS Catalysis (2021), 11 (8), 4784-4798CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
    Adjusting hydrocarbon product distributions in the Fischer-Tropsch (FT) synthesis is of notable significance in the context of so-called X-to-liqs. (XTL) technologies. While cobalt catalysts are selective to long-chain paraffin precursors for synthetic jet- and diesel-fuels, lighter (C10-) alkane condensates are less valuable for fuel prodn. Alternatively, iron carbide-based catalysts are suitable for the coprodn. of paraffinic waxes alongside liq. (and gaseous) olefin chems.; however, their activity for the water-gas-shift reaction (WGSR) is notoriously detrimental when hydrogen-rich syngas feeds, for example, derived from (unconventional) natural gas, are to be converted. Herein the roles of pore architecture and oxide promoters of Lewis basic character on CoRu/Al2O3 FT catalysts are systematically addressed, targeting the development of catalysts with unusually high selectivity to liq. olefins. Both alkali and lanthanide oxides lead to a decrease in turnover frequency. The latter, particularly PrOx, prove effective to boost the selectivity to liq. (C5-10) olefins without undesired WGSR activity. In situ CO-FTIR spectroscopy suggests a dual promotion via both electronic modification of surface Co sites and the inhibition of Lewis acidity on the support, which has direct implications for double-bond isomerization reactivity and thus the regioisomery of liq. olefin products. D. functional theory calcns. ascribe oxide promotion to an enhanced competitive adsorption of mol. CO vs. hydrogen and olefins on oxide-decorated cobalt surfaces, dampening (secondary) olefin hydrogenation, and suggest an exacerbated metal surface carbophilicity to underlie the undesired induction of WGSR activity by strongly electron-donating alkali oxide promoters. Enhanced pore mol. transport within a multimodal meso-macroporous architecture in combination with PrOx as promoter, at an optimal surface loading of 1 Prat nm-2, results in an unconventional product distribution, reconciling benefits intrinsic to Co- and Fe-based FT catalysts, resp. A chain-growth probability of 0.75, and thus >70 C% selectivity to C5+ products, is achieved alongside lighter hydrocarbon (C5-10) condensates that are significantly enriched in added-value chems. (67 C%), predominantly α-olefins but also linear alcs., remarkably with essentially no CO2 side-prodn. (<1%). Such unusual product distributions, integrating precursors for synthetic fuels and liq. platform chems., might be desired to diversify the scope and improve the economics of small-scale gas- and biomass-to-liq. processes.
  5. 5
    Hellier, P.; Talibi, M.; Eveleigh, A.; Ladommatos, N. An Overview of the Effects of Fuel Molecular Structure on the Combustion and Emissions Characteristics of Compression Ignition Engines. Proc. Inst. Mech. Eng., Part D 2018, 232, 90– 105,  DOI: 10.1177/0954407016687453
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    An overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines
    Hellier, Paul; Talibi, Midhat; Eveleigh, Aaron; Ladommatos, Nicos
    Proceedings of the Institution of Mechanical Engineers, Part D: Journal of Automobile Engineering (2018), 232 (1), 90-105CODEN: PMDEEA; ISSN:0954-4070. (Sage Publications Ltd.)
    Future fuels for compression ignition engines will be required both to reduce the anthropogenic carbon dioxide emissions from fossil sources and to contribute to the redns. in the exhaust levels of pollutants, such as nitrogen oxides and particulate matter. Via various processes of biol., chem. and phys. conversion, feedstocks such as lignocellulosic biomass and photosynthetic micro-organisms will yield a wide variety of potential fuel mols. Furthermore, modification of the prodn. processes may allow the targeted manuf. of fuels of specific mol. structure. This paper therefore presents an overview of the effects of fuel mol. structure on the combustion and emissions characteristics of compression ignition engines, highlighting in particular the submol. features common to a variety of potential fuels. An increase in the straight-chain length of the alkyl moiety reduces the duration of ignition delay, and the introduction of double bonds or branching to an alkyl moiety both increase ignition delay. The movement of a double bond towards the center of an alkyl chain, or the addn. of oxygen to a mol., can both increase and decrease the duration of ignition delay dependent on the overall fuel structure. Nitrogen oxide emissions are primarily influenced by the duration of fuel ignition delay, but in the case of hydrogen and methane pilot-ignited premixed combustion arise only at flame temps. sufficiently high for thermal prodn. An increase in arom. ring no. and phys. properties such as the fuel b.p. increase particulate matter emissions at const. combustion phasing.
  6. 6
    Choudhury, H. A.; Intikhab, S.; Kalakul, S.; Khan, M.; Tafreshi, R.; Gani, R.; Elbashir, N. O. Designing a Surrogate Fuel for Gas-to-Liquid Derived Diesel. Energy Fuels 2017, 31, 11266– 11279,  DOI: 10.1021/acs.energyfuels.7b00274
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    Designing a Surrogate Fuel for Gas-to-Liquid Derived Diesel
    Choudhury, H. A.; Intikhab, S.; Kalakul, S.; Khan, M.; Tafreshi, R.; Gani, R.; Elbashir, N. O.
    Energy & Fuels (2017), 31 (10), 11266-11279CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)
    Synthetic diesel fuel produced from natural gas via gas-to-liq. (GTL) technol. is referred to as ultraclean fuel but is still challenged for full certification as diesel fuel. GTL diesel lacks certain hydrocarbons and chem. constituents, which although are benign to the environment, result in a trade-off in performance when used in a diesel engine. To boost GTL diesel physicochem. properties and thereby enable its use in conventional diesel engines, GTL diesel needs improvement. This can be achieved by mixing suitable additives to the GTL diesel and through the development of surrogate fuels that have fewer components. Screening of thousands of additives is a tedious task and can be done efficiently via computer based modeling to quickly and reliably identify a small no. of promising candidates. These models are used to guide the formulation of five surrogates and predict their physicochem. properties. These surrogates are further verified using rigorous math. tools as well as through advanced exptl. techniques. An optimal surrogate MI-5 is identified, which closely mimics GTL diesel-conventional diesel blends in terms of its physicochem. properties. An engine study for the surrogate is also performed to understand the effect of physicochem. properties on combustion as well as the emission behavior of the fuel. MI-5 exhibited an optimal torque at higher load conditions. A redn. of 11.26% NOx emission for MI-5 is obsd. when compared to conventional fuel. At higher loads, diesel fuel surpasses the total hydrocarbon (THC) emissions for both the surrogate and the GTL fuel. No significant variation in CO and CO2 emissions for MI-5, GTL diesel and conventional diesel is obsd. Anal. of combustion as well as emission behavior of the fuels helps to understand the role of physicochem. properties on the performance of the fuel.
  7. 7
    Graziano, B.; Schönfeld, S.; Heuser, B.; Pelerin, D. 1-Octanol as CO2-Neutral Fuel for Commercial Vehicle Applications. ATZheavy Duty Worldwide 2020, 13, 36– 41,  DOI: 10.1007/s35746-020-0114-7
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    Kohlpaintner, C.; Schulte, M.; Falbe, J.; Lappe, P.; Weber, J.; Frey, G. D. Aldehydes, Aliphatic. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2013.
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    Püschel, S.; Störtte, S.; Topphoff, J.; Vorholt, A. J.; Leitner, W. Green Process Design for Reductive Hydroformylation of Renewable Olefin Cuts for Drop-in Diesel Fuels. ChemSusChem 2021, 14, 5226– 5234,  DOI: 10.1002/cssc.202100929
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    9
    Green Process Design for Reductive Hydroformylation of Renewable Olefin Cuts for Drop-In Diesel Fuels
    Pueschel, Sebastian; Stortte, Sven; Topphoff, Johanna; Vorholt, Andreas J.; Leitner, Walter
    ChemSusChem (2021), 14 (23), 5226-5234CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    CO2-neutral fuels are a way to cleaner and more sustainable mobility. Utilization of bio-syngas via Fischer-Tropsch (FT) synthesis represents an interesting route for the prodn. of tailormade biofuels. Recent developments in FT catalyst research led to olefin-enriched products, enabling the synthesis of alc.-enriched fuels by reductive hydroformylation of the C=C bond. Several alcs. have already proven to be suitable fuel additives with favorable combustion behavior. Here, a hydroformylation-hydrogenation sequence of FT-olefin-paraffin mixts. was investigated as a potential route to alcs. A liq.-liq. biphasic system with a rhodium/3,3',3''-phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS) catalyst system was chosen for effective catalyst recycling. After optimizing reaction conditions with a model substrate consisting of 1-octene and n-heptane the conversion of an actual olefin-contg. C5-C10 FT product fraction to alcs. in continuously operated processes for 37 h was achieved with a total turnover no. of 23679.
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    Anastas, P.; Eghbali, N. Green Chemistry: Principles and Practice. Chem. Soc. Rev. 2010, 39, 301– 312,  DOI: 10.1039/b918763b
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    Green Chemistry: Principles and Practice
    Anastas, Paul; Eghbali, Nicolas
    Chemical Society Reviews (2010), 39 (1), 301-312CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. Green Chem. is a relatively new emerging field that strives to work at the mol. level to achieve sustainability. The field has received widespread interest in the past decade due to its ability to harness chem. innovation to meet environmental and economic goals simultaneously. Green Chem. has a framework of a cohesive set of Twelve Principles, which have been systematically surveyed in this crit. review. This article covers the concepts of design and the scientific philosophy of Green Chem. with a set of illustrative examples. Future trends in Green Chem. are discussed with the challenge of using the Principles as a cohesive design system (93 refs.).
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    Fogg, D. E.; Dos Santos, E. N. Tandem Catalysis: A Taxonomy and Illustrative Review. Coord. Chem. Rev. 2004, 248, 2365– 2379,  DOI: 10.1016/j.ccr.2004.05.012
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    Tandem catalysis: a taxonomy and illustrative review
    Fogg, Deryn E.; dos Santos, Eduardo N.
    Coordination Chemistry Reviews (2004), 248 (21-24), 2365-2379CODEN: CCHRAM; ISSN:0010-8545. (Elsevier B.V.)
    A review. A scheme is advanced for the classification of 1-pot, coupled catalytic transformations, which distinguishes between 1-pot, domino/cascade, and tandem catalysis. The last of these is divided into three subclasses: orthogonal, auto-tandem, and assisted tandem catalysis. The proposed taxonomy, and the potential of tandem catalysis in org. synthesis, are illustrated with examples drawn from olefin metathesis and hydroformylation chem.
  12. 12
    Rodrigues, F. M. S.; Kucmierczyk, P. K.; Pineiro, M.; Jackstell, R.; Franke, R.; Pereira, M. M.; Beller, M. Dual Rh–Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols. ChemSusChem 2018, 11, 2310– 2314,  DOI: 10.1002/cssc.201800488
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    Dual Rh-Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols
    Rodrigues, Fabio M. S.; Kucmierczyk, Peter K.; Pineiro, Marta; Jackstell, Ralf; Franke, Robert; Pereira, Mariette M.; Beller, Matthias
    ChemSusChem (2018), 11 (14), 2310-2314CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    An active and selective dual catalytic system to promote domino hydroformylation-redn. reactions is described. Apart from terminal, di- and trisubstituted olefins, for the first time the less active internal C-C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3-dimethylbut-2-ene is converted into the corresponding n-alc. with high yield (90 %) as well as regio- and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru-based Shvo's complex. A variety of arom. and aliph. alkenes can be directly used to obtain mainly linear alcs.
  13. 13
    Takahashi, K.; Yamashita, M.; Ichihara, T.; Nakano, K.; Nozaki, K. High-Yielding Tandem Hydroformylation/Hydrogenation of a Terminal Olefin to Produce a Linear Alcohol Using a Rh/Ru Dual Catalyst System. Angew. Chem., Int. Ed. 2010, 49, 4488– 4490,  DOI: 10.1002/anie.201001327
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    13
    High-yielding tandem hydroformylation/hydrogenation of a terminal olefin to produce a linear alcohol using a Rh/Ru dual catalyst system
    Takahashi, Kohei; Yamashita, Makoto; Ichihara, Takeo; Nakano, Koji; Nozaki, Kyoko
    Angewandte Chemie, International Edition (2010), 49 (26), 4488-4490, S4488/1-S4488/12CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
    1-Decene undergoes highly regio- and chemoselective tandem hydroformylation-redn. by use of binuclear ruthenium hydrido- and hydrogen bond-bridged tetraphenylcyclopentadienone-hydroxycyclopentadienyl complex (Shvo's catalyst) as a hydrogenation catalyst and rhodium acetylacetonate-Xantphos hydroformylation catalyst in a one-pot reaction. The optimized yields of 1-undecanol reached 90% with n/i ratio of 22 and aldehyde content of 1%.
  14. 14
    Diebolt, O.; Müller, C.; Vogt, D. “On-Water” Rhodium-Catalysed Hydroformylation for the Production of Linear Alcohols. Catal. Sci. Technol. 2012, 2, 773– 777,  DOI: 10.1039/c2cy00450j
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    "On-water" rhodium-catalysed hydroformylation for the production of linear alcohols
    Diebolt, Olivier; Mueller, Christian; Vogt, Dieter
    Catalysis Science & Technology (2012), 2 (4), 773-777CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
    Optimization of the reaction conditions for the rhodium-catalyzed aldehyde hydrogenation under hydroformylation conditions showed that water used as co-solvent enhances both rate and selectivity towards primary alcs. One-pot hydroformylation-hydrogenation using rhodium as the only transition metal yielded alcs. in excellent selectivities and good linearities.
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    van Winkle, J. L.; Lorenzo, S.; Morris, R. C.; Mason, R. F. Single Stage Hydroformylation of Olefins to Alcohols. U.S. Patent US3420898A1969.
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    Slaugh, L. H.; Mullineaux, R. D. Hydroformylation of Olefins. U.S. Patent US3239569A1966.
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    Fuchs, S.; Lichte, D.; Dittmar, M.; Meier, G.; Strutz, H.; Behr, A.; Vorholt, A. J. Tertiary Amines as Ligands in a Four-Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers. ChemCatChem 2017, 9, 1436– 1441,  DOI: 10.1002/cctc.201601518
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    Tertiary Amines as Ligands in a Four-Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers
    Fuchs, Sarah; Lichte, Dominik; Dittmar, Morten; Meier, Gregor; Strutz, Heinz; Behr, Arno; Vorholt, Andreas J.
    ChemCatChem (2017), 9 (8), 1436-1441CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A catalyst system [dirhodium tetraoctanoate (Rh2(oct)4) and Et3N in toluene] is developed for the chemoselective tandem hydroformylation and hydrogenation of dicyclopentadiene under 70 bar H2 and CO at 120° to yield tricyclodecanedimethanols; under optimized conditions, a 79% yield of diols was obtained without the formation of olefin hydrogenation byproducts. 1,3-Divinylbenzene and 5-vinyl-2-norbornene yielded the corresponding dimethanols under similar conditions with 8 and 60% of aldol side products formed, resp.; tandem hydroformylation and hydrogenation of 4-vinylcyclohexene and norbornadiene yielded aldol adducts as the major or exclusive products. The catalyst was recycled by water extn. of the product from the reaction mixt. and recycling of the toluene phase.
  18. 18
    Fuchs, S.; Lichte, D.; Jolmes, T.; Rösler, T.; Meier, G.; Strutz, H.; Behr, A.; Vorholt, A. J. Synthesis of Industrial Primary Diamines via Intermediate Diols – Combining Hydroformylation, Hydrogenation and Amination. ChemCatChem 2018, 10, 4126– 4133,  DOI: 10.1002/cctc.201800950
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    Synthesis of Industrial Primary Diamines via Intermediate Diols - Combining Hydroformylation, Hydrogenation and Amination
    Fuchs, Sarah; Lichte, Dominik; Jolmes, Tristan; Roesler, Thorsten; Meier, Gregor; Strutz, Heinz; Behr, Arno; J. Vorholt, Andreas
    ChemCatChem (2018), 10 (18), 4126-4133CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Dicyclopentadiene underwent hydrohydroxymethylation (via hydroformylation and hydrogenation) followed by amination with ammonia in the presence of combinations of dirhodium tetraoctanoate, RuHCl(CO)(PPh3)3, Xantphos, and Et3N in tert-amyl alc. to yield the tricyclodecanedimethanamine I (as a mixt. of its four regioisomers); the hydrohydroxymethylation and amination reactions were performed both in sequence and in tandem. High yields of both the hydrohydroxymethylation and amination reactions were obtained, but the presence of rhodium in the amination reaction or of ruthenium in the hydrohydroxymethylation reaction inhibits the reactions and worsens their selectivities. Using sequential hydrohydroxymethylation and amination reactions, I was obtained in 88% yield.
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    Gorbunov, D.; Nenasheva, M.; Naranov, E.; Maximov, A.; Rosenberg, E.; Karakhanov, E. Tandem Hydroformylation/Hydrogenation over Novel Immobilized Rh-Containing Catalysts Based on Tertiary Amine-Functionalized Hybrid Inorganic-Organic Materials. Appl. Catal., A 2021, 623, 118266  DOI: 10.1016/j.apcata.2021.118266
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    19
    Tandem hydroformylation/hydrogenation over novel immobilized Rh-containing catalysts based on tertiary amine-functionalized hybrid inorganic-organic materials
    Gorbunov, Dmitry; Nenasheva, Maria; Naranov, Evgeny; Maximov, Anton; Rosenberg, Edward; Karakhanov, Eduard
    Applied Catalysis, A: General (2021), 623 (), 118266CODEN: ACAGE4; ISSN:0926-860X. (Elsevier B.V.)
    Non-phosphorous rhodium-contg. catalysts for direct conversion of olefins to alcs. via tandem hydroformylation/hydrogenation have been designed and synthesized. Interaction between Rh(acac)(CO)2 and tertiary amino groups on the surface of mesoporous hybrid org.-inorg. supports yielded materials which were successfully used in the tandem process. Data obtained for a selected catalyst KN demonstrate that rhodium is in the Rh+1 state highly dispersed on the surface and is bonded with nitrogen atoms both before and after use. Evaluation of the catalytic performance shows high activity (hydroformylation TOF 312 h-1), chemoselectivity and stable hydroformylation yield at least in the first 5 cycles with a decrease in alc. selectivity. The influence of temp., reaction time, total pressure, and molar CO/H2 ratio of syngas on oxygenate yields is described. Type of the hydroformylation active sites and possible pathways for the obsd. decrease in hydrogenation are discussed.
  20. 20
    Furst, M. R. L.; Korkmaz, V.; Gaide, T.; Seidensticker, T.; Behr, A.; Vorholt, A. J. Tandem Reductive Hydroformylation of Castor Oil Derived Substrates and Catalyst Recycling by Selective Product Crystallization. ChemCatChem 2017, 9, 4319– 4323,  DOI: 10.1002/cctc.201700965
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    Tandem Reductive Hydroformylation of Castor Oil Derived Substrates and Catalyst Recycling by Selective Product Crystallization
    Furst, Marc R. L.; Korkmaz, Vedat; Gaide, Tom; Seidensticker, Thomas; Behr, Arno; Vorholt, Andreas J.
    ChemCatChem (2017), 9 (23), 4319-4323CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
    An orthogonal tandem catalytic system consisting of rhodium and ruthenium complexes yielded linear C12 α,ω-bifunctional compds. from com., castor oil derived renewable substrates. With aldehyde yields up to 88 % and selectivities to the linear species of up to 95 %, this approach is direct and atom economic and provides easy access to potential polymer precursors for polycondensates. Addnl., a straightforward method for selective product crystn. was developed, which enabled recycling of the tandem catalytic system for two runs with excellent activity and simultaneously provided a high-purity product.
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    Rösler, T.; Ehmann, K. R.; Köhnke, K.; Leutzsch, M.; Wessel, N.; Vorholt, A. J.; Leitner, W. Reductive Hydroformylation With A Selective And Highly Active Rhodium Amine System. J. Catal. 2021, 400, 234– 243,  DOI: 10.1016/j.jcat.2021.06.001
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    Cheung, L. L. W.; Vasapollo, G.; Alper, H. Synthesis of Alcohols via a Rhodium-Catalyzed Hydroformylation-Reduction Sequence Using Tertiary Bidentate Amine Ligands. Adv. Synth. Catal. 2012, 354, 2019– 2022,  DOI: 10.1002/adsc.201200053
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    22
    Synthesis of Alcohols via a Rhodium-Catalyzed Hydroformylation - Reduction Sequence using Tertiary Bidentate Amine Ligands
    Cheung, Lawrence L. W.; Vasapollo, Giuseppe; Alper, Howard
    Advanced Synthesis & Catalysis (2012), 354 (10), 2019-2022, S2019/1-S2019/16CODEN: ASCAF7; ISSN:1615-4150. (Wiley-VCH Verlag GmbH & Co. KGaA)
    The synthesis of alcs. from arom. olefins is described using a rhodium-catalyzed hydroformylation-redn. sequence with the assistance of a tertiary diamine ligand. The alcs., e.g., I (R = H, Me, MeO, Ph, Cl), are produced in excellent branched to linear ratios and in good to excellent isolated yields. In all cases no aldehyde product, from hydroformylation, or alkyl product, from olefin redn., was detected.
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    Vanbésien, T.; Monflier, E.; Hapiot, F. Rhodium-Catalyzed One Pot Synthesis of Hydroxymethylated Triglycerides. Green Chem. 2016, 18, 6687– 6694,  DOI: 10.1039/c6gc02706g
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    Rhodium-catalyzed one pot synthesis of hydroxymethylated triglycerides
    Vanbesien, T.; Monflier, E.; Hapiot, F.
    Green Chemistry (2016), 18 (24), 6687-6694CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)
    The direct functionalization of the carbon-carbon double bonds of triglycerides is of major interest to access biosourced building blocks with unique mol. and functional properties. In this study, we described the synthesis of trihydroxylated triglycerides via a hydrohydroxymethylation reaction, which consists of two consecutive Rh-catalyzed reactions, namely, a hydroformylation followed by a consecutive redn. of formyl groups. Contrary to two-step procedures described in the literature, no phosphane was used to coordinate Rh-species, thus giving our strategy an industrial potential. Tertiary amines were used as ligands to promote the hydrohydroxymethylation reaction. The Rh/amine-catalyst proved to be active both in hydroformylation of the carbon-carbon double bond and redn. of the resulting aldehyde into alc. The proportion of hydroxyl groups grafted onto triglyceride fatty chains was optimized by a careful choice of exptl. conditions, esp. the nature and the amt. of the tertiary amine, the reaction temp., and the CO/H2 pressure.
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    Ternel, J.; Lopes, A.; Sauthier, M.; Buffe, C.; Wiatz, V.; Bricout, H.; Tilloy, S.; Monflier, E. Reductive Hydroformylation of Isosorbide Diallyl Ether. Molecules 2021, 26, 7322  DOI: 10.3390/molecules26237322
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    Reductive Hydroformylation of Isosorbide Diallyl Ether
    Ternel, Jeremy; Lopes, Adrien; Sauthier, Mathieu; Buffe, Clothilde; Wiatz, Vincent; Bricout, Herve; Tilloy, Sebastien; Monflier, Eric
    Molecules (2021), 26 (23), 7322CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
    Herein, hydroformylation of isosorbide diallyl ether using a rhodium/amine catalytic system has been studied. The highest yield of bis-primary alcs. obtained was equal to 79%.
  25. 25
    Püschel, S.; Hammami, E.; Ehmann, K. R.; Rösler, T.; Leitner, W.; Vorholt, A. J. Auto-Tandem Catalytic Reductive Hydroformylation with Continuous Multiphase Catalyst Recycling. Catal. Sci. Technol. 2022, 12, 728– 736,  DOI: 10.1039/D1CY02000E
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    Auto-tandem catalytic reductive hydroformylation with continuous multiphase catalyst recycling
    Pueschel, Sebastian; Hammami, Enes; Roesler, Thorsten; Ehmann, Kira R.; Vorholt, Andreas J.; Leitner, Walter
    Catalysis Science & Technology (2022), 12 (3), 728-736CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
    The prodn. of alcs. from olefin-enriched Fischer-Tropsch products represents a promising route for CO2-neutral bio-synthetic fuels. Tandem-catalytic systems as alternatives for the conventional two-step prodn. of long-chain alcs. are attractive in terms of energy and resource efficiency. Herein, we present the first rhodium-based catalytic system capable of direct conversion of olefins to alcs. in a biphasic liq./liq. system. After optimizing the reaction conditions for the biphasic operation, an alc. selectivity of up to 64% was achieved, while aldehydes and olefin isomers were obsd. as main byproducts. By employing water-sol. alkanolamines, the catalyst is immobilized in a water phase and can be easily sepd. from the product contg. an org. phase with a rhodium loss of as low as 0.1%. After investigation of various reaction parameters, a TON of 128 in batch operation was achieved. Furthermore, the developed catalyst recycling strategy was implemented in a continuously operated miniplant, reaching a TTON for alc. prodn. of 1236 after 50 h.
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    Großeheilmann, J.; Vanderveen, J. R.; Jessop, P. G.; Kragl, U. Switchable-Hydrophilicity Solvents for Product Isolation and Catalyst Recycling in Organocatalysis. ChemSusChem 2016, 9, 696– 702,  DOI: 10.1002/cssc.201501654
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    Switchable-Hydrophilicity Solvents for Product Isolation and Catalyst Recycling in Organocatalysis
    Grosseheilmann, Julia; Vanderveen, Jesse R.; Jessop, Philip G.; Kragl, Udo
    ChemSusChem (2016), 9 (7), 696-702CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    Switchable-hydrophilicity solvents (SHSs) are solvents that can switch reversibly between a water-miscible state to a state that forms a biphasic mixt. with water. In this case study, SHSs have been studied for easy product/catalyst sepn. as well as catalyst recycling. A series of tertiary amine SHSs have been identified for the extn. of the hydrophilic product from the postreaction mixt. Here, the authors detd. high extn. efficiencies for the product (>84%) and low extn. rates for the catalyst (<0.1%). With the catalyst recycling expts., we isolated the product in high purity (>98%) without further purifn. steps. At the same time, the catalyst was reused without any loss of activity (>91% enantiomeric excess, >99% yield) four times. Furthermore, the authors optimized the extn. efficiency by working with a microextractor. In addn., with the use of a falling-film microreactor, the authors obtained the product with high enantioselectivity by working at ambient conditions.
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    Many CO2-responsive species, including many of the CO2-switchable surfactants, solvents, solutes, gels, colloids, and surfaces, rely on the ability of CO2 to lower the pH of water. Uncharged basic groups on the CO2-responsive species are therefore converted from a neutral state to a protonated cationic state (a bicarbonate salt), which causes dramatic and useful changes to the properties of the species. However, this switching process only works correctly if a basic group of appropriate basicity has been selected. This article presents a comprehensive guide to the selection of basic groups for CO2-switchable species for use in water. The appropriate basicity, as measured by the pKaH (the pKa of the protonated compd.), is a function of the concn. of the switchable species, the temp., the pressure of CO2, the presence or absence of an org. liq. phase, and the soly. of the neutral form of the compd.
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    Aq./org. biphasic catalysis allows easy sepn. of a homogeneous catalyst from product, but is often inefficient when hydrophobic substrates are used. A system based on switchable water is monophasic in the absence of CO2 and biphasic in its presence. Catalysis can be performed in the monophasic solvent, and then switched to a biphasic system, sepg. catalyst from product. Removal of CO2 allows for easy recycling of the catalyst. Hydroformylations have been achieved using this solvent system. The catalyst was recycled several times with minimal loss of activity.
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    Künnemann, K. U.; Bianga, J.; Scheel, R.; Seidensticker, T.; Dreimann, J. M.; Vogt, D. Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System. Org. Process Res. Dev. 2020, 24, 41– 49,  DOI: 10.1021/acs.oprd.9b00409
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    Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System
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    Organic Process Research & Development (2020), 24 (1), 41-49CODEN: OPRDFK; ISSN:1083-6160. (American Chemical Society)
    For the first time, the successful application of the homogeneously catalyzed reductive amination in a thermomorphic multiphase system (TMS) and the first reported scale-up of this reaction into a continuous process, which recovers and recycles the homogeneous catalyst in flow, is presented. Herein, the model substrate 1-decanal reacts with the secondary amine diethylamine to form the corresponding product N,N-diethyldecylamine. A thermomorphic multiphase system (TMS) is established as a recycling strategy to recover and reuse the catalyst for the continuous process. After screening different solvents for the TMS and optimizing the reaction conditions in batch mode, the recycling of the rhodium catalyst was realized in a fully automated miniplant. Parameters influencing the stability of the process were identified and optimized to develop the continuous process. The process was operated in a steady state over 90 h with yields >90% of the desired product and low catalyst leaching <1%/h.
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    N,N-Dimethylethanolamine (DMEA) is a promising absorbent due to the relative higher reaction rate and high capacity for CO2 capture. In this work, the CO2 absorption performance into aq. DMEA soln. using a polytetrafluoroethylene (PTFE) hollow-fiber membrane contactor (HFMC) was investigated exptl. and numerically. The CO2 absorption fluxes were detd. under various important operating parameters, including liq. velocity, gas velocity, liq. feed temp., CO2 partial pressure, and CO2 loading in liq. phase. In addn., a 2D steady-state math. model was established to predict the CO2 absorption flux in two operation modes, non-wetted and partially wetted modes, and was validated by using the CO2 absorption into water and aq. MEA soln. The exptl. and simulated results revealed that the CO2 absorption flux can be enhanced by increasing liq. velocity, liq.-phase temp., and amine concn. in a moderate range. Also, the CO2 absorption flux will increase with the increasing gas velocity and CO2 partial pressure but decrease with increasing CO2 loading in the liq. phase. In addn., the membrane wetting can cause a severe deterioration in the CO2 absorption performance even with a slight membrane wetting. The CO2 absorption fluxes for CO2 absorption into DMEA solns. show the good agreement with or are closer to the simulated data with the membrane wetting of 10% under the same operational conditions, with the av. abs. relative deviation (AARD) of 5.02%. Furthermore, the obtained radial and axial CO2 concn. profiles from the math. model were also discussed to further understand the CO2 absorption process.
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    A review. The numerous approaches for the catalytic synthesis of alkyl alcs. using an intermediate hydroformylation step are reviewed. One main strategy is a sequence where hydroformylation and hydrogenation are carried out step by step. More challenging are hydroformylation reactions under reducing conditions. In this regard, the transformation can be assisted by two different catalysts or one single catalyst (tandem reaction). A particular challenge in this respect is the undesired olefin hydrogenation. Sequences where hydroformylation is combined with a subsequent aldol reaction are of huge economic importance. The different performances of the catalytic systems on the basis of rhodium, cobalt, palladium, and ruthenium are described together with typical org. ligands, reaction conditions, and selected applications.
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    Becquet, C.; Berche, F.; Bricout, H.; Monflier, E.; Tilloy, S. Hydrohydroxymethylation of Ethyl Ricinoleate and Castor Oil. ACS Sustainable Chem. Eng. 2021, 9, 9444– 9454,  DOI: 10.1021/acssuschemeng.1c02924
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    Hydrohydroxymethylation of Ethyl Ricinoleate and Castor Oil
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    ACS Sustainable Chemistry & Engineering (2021), 9 (28), 9444-9454CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
    The direct functionalization of the carbon-carbon double bonds of castor oil and its derivs. is of major interest to access biosourced building blocks. In particular, polyol derivs. can be produced in this way and find application in the field of bio-based polyesters and polyurethanes. In this study, we described the synthesis of polyhydroxylated derivs. via a hydrohydroxymethylation reaction consisting of two consecutive Rh-catalyzed reactions: a hydroformylation reaction followed by a hydrogenation reaction of formyl groups. A catalytic system based on Rh(acac)(CO)2 and a trialkylamine proved to be active both in hydroformylation of carbon-carbon double bonds and redn. of the resulting aldehydes into primary alcs. By optimizing the reaction conditions, yields in alcs. of 74 and 80% were reached for castor oil and Et ricinoleate, resp.
  35. 35
    Nenasheva, M.; Gorbunov, D.; Karasaeva, M.; Maximov, A.; Karakhanov, E. Non-Phosphorus Recyclable Rh / Triethanolamine Catalytic System for Tandem Hydroformylation / Hydrogenation and Hydroaminomethylation of Olefins under Biphasic Conditions. Mol. Catal. 2021, 516, 112010  DOI: 10.1016/j.mcat.2021.112010
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    Non-phosphorus recyclable Rh/triethanolamine catalytic system for tandem hydroformylation/hydrogenation and hydroaminomethylation of olefins under biphasic conditions
    Nenasheva, Maria; Gorbunov, Dmitry; Karasaeva, Moldir; Maximov, Anton; Karakhanov, Eduard
    Molecular Catalysis (2021), 516 (), 112010CODEN: MCOADH ISSN:. (Elsevier B.V.)
    For the first time, one-pot hydroformylation/hydrogenation and hydroaminomethylation of olefins are performed under biphasic conditions using a non-phosphorous Rh/amine catalytic system. Available, cheap, and non-toxic triethanolamine was found to be an effective water-sol. ligand, providing easy sepn. and reuses of the catalytic system without significant loss in activity.

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  • Abstract

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    Figure 1

    Figure 1. General concept of the CO2-switchable phase behavior.

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    Scheme 1

    Scheme 1. Reductive Hydroformylation Reaction Network
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    Figure 2

    Figure 2. Product recovery and amine leaching with varying WAR and CO2 loading. Separation conditions: Tsep = 25 °C, tsep = 5 min, product recovery = nalcohol, second phase/nalcohol, total, water–amine ratio (WAR) = mWater/mDEAE, and Y = simulated alcohol yield in the surrogate mixture.

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    Figure 3

    Figure 3. Variation of catalyst concentration. Reaction conditions: n1-octene = 38.4 mmol (6 mL), Vn-heptane = 6 mL, T = 100 °C, tR = 1.5 h, p = 30 bar, CO/H2 = 1:2, φorg = 0.4, Vliq = 30 mL, water–amine ratio = 0.3, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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    Figure 4

    Figure 4. Variation of Syngas pressure and composition. Reaction conditions: ccat = 0.25 mol %, n1-octene = 38.4 mmol (6 mL), nRh = 0.096 mmol, Vn-heptane = 6 mL, T = 100 °C, tR = 1.5 h, φorg = 0.4, Vliq = 30 mL, water–amine ratio = 0.3, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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    Figure 5

    Figure 5. Variation of the reaction temperature. Reaction conditions: ccat = 0.25 mol %, n1-octene = 38.4 mmol (6 mL), nRh = 0.096 mmol, Vn-heptane = 6 mL, p = 60 bar, CO/H2 = 1:2, tR = 1.5 h, φorg = 0.4, Vliq = 30 mL, water–amine ratio = 0.3, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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    Figure 6

    Figure 6. Time profile experiments with varying water/amine ratios, syngas pressure, and catalyst concentration. Conditions for all graphs: reaction conditions: n1-octene = 166.4 mmol (26 mL), nRh = 0.416 mmol, Vn-heptane = 26 mL, T = 140 °C, CO/H2 = 1:2, φorg = 0.4, Vliq = 130 mL, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2].

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    Figure 7

    Figure 7. Switchable solvent system catalyst recycling concept.

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    Figure 8

    Figure 8. Proof-of-concept recycling experiment. Reaction conditions: ccat = 0.25 mol %, n1-octene = 166.4 mmol (26 mL), nRh = 0.416 mmol, Vn-heptane = 26 mL, T = 140 °C, p = 90 bar, CO/H2 = 1:2, tR = 1.5 h, φorg = 0.4, Vliq = 130 mL, water–amine ratio = 0.5, r = 2000 min–1, and catalyst = [Rh(acac)(CO)2]; separation conditions: Tsep = 25 °C, tsep = 5 min, nCO2/nDEAE = 2.0, Trev = 70 °C, and trev = 20 min.

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    Figure 9

    Figure 9. Recycling experiment with reduced CO2 loading in phase separation. Reaction conditions: ccat = 0.25 mol %, n1-octene = 166.4 mmol (26 mL), nRh = 0.416 mmol, Vn-heptane = 26 mL, T = 140 °C, p = 90 bar, CO/H2 = 1:2, tR = 3 h, φorg = 0.4, Vliq = 50 mL, water–amine ratio = 0.5, n = 2000 min–1, and catalyst = [Rh(acac)(CO)2]; separation conditions: Tsep = 25 °C, tsep = 5 min, nCO2/nDEAE = 0.9, Trev = 70 °C, and trev = 20 min.

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  • References

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      Garcia, Antonio; Monsalve-Serrano, Javier; Villalta, David; Zubel, Marius; Pischinger, Stefan
      Energy Conversion and Management (2018), 177 (), 563-571CODEN: ECMADL; ISSN:0196-8904. (Elsevier Ltd.)
      This exptl. work evaluates the potential of 1-octanol, di-Bu ether and three intermediate blends as substitutes of the diesel fuel to be used in compression ignition engines. For this purpose, performance and engine-out emissions measurements have been done in a single-cylinder engine of 0.39 L displacement and 15:1 compression ratio at four engine operating conditions representative of the new European driving cycle (NEDC) driving cycle. The tests have been done keeping const. the NOx emissions and combustion center for all the fuels at each operating point. To achieve this, the exhaust gas recirculation rate and the start of injection timing were modified simultaneously for each fuel tested, while the rest of the engine settings were kept const. All the biomass-derived fuels have the same oxygen content but substantially different cetane no. and volatility. The results show that, for the same NOx levels, all the fuels allow a substantial redn. of the soot emissions vs. diesel due to both the higher oxygen content in the fuel mol. and/or the extended mixing time achieved because of the lower fuel reactivity. In terms of efficiency, all the alternative fuels improve the fuel-to-work conversion efficiency. This benefit comes from decreasing the heat transfer in a greater way than the exhaust losses increase. Moreover, in general terms, all the fuels promote a redn. of the combustion losses to halve of those found with diesel.
    3. 3
      Janssen, A. J.; Kremer, F. W.; Baron, J. H.; Muether, M.; Pischinger, S.; Klankermayer, J. Tailor-Made Fuels from Biomass for Homogeneous Low-Temperature Diesel Combustion. Energy Fuels 2011, 25, 4734– 4744,  DOI: 10.1021/ef2010139
      3
      Tailor-Made Fuels from Biomass for Homogeneous Low-Temperature Diesel Combustion
      Janssen, Andreas J.; Kremer, Florian W.; Baron, Jan H.; Muether, Martin; Pischinger, Stefan; Klankermayer, Juergen
      Energy & Fuels (2011), 25 (10), 4734-4744CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)
      The use of modern biofuels in mobile applications has an enormous potential to reduce greenhouse gases as well as engine pollutant emissions, such as soot or nitrogen oxides. This beneficial effect is directly related to the mol. structure of the biofuel as a product of an optimized prodn. process. To understand the influence and emission redn. potential of the large variety of different fuel properties, this study aims to identify desirable fuel characteristics and define optimized biofuel components. In a first step, a literature survey is carried out, focusing on the impact of the cetane no., boiling characteristics, and arom. and oxygen contents on the diesel combustion process. The incorporated investigations that analyze the combustion behavior, engine efficiency, and emission performance underline the potential of tailoring fuels to desired properties. From this foundation, a model-based anal. of desired fuel properties was conducted, using a large database with 32 different fuels (single mols. and fuel mixts.). With multiple correlation methods, different fuel properties can be used to predict the emission performance of the engine. The following fuel optimization based on emission performance and engine efficiency results in ideal fuel properties for diesel engine combustion. As it turns out, a blend of 2-methyltetrahydrofurane (2-MTHF) (which can be derived from cellulose) blended with di-n-butylether complies with the desired fuel properties, which were defined before. In combination with an improved homogeneous low-temp. combustion process and an increased ignition delay, a nearly soot-free diesel combustion over a wide load range is realized. The oxygenated fuel enables increased exhaust gas recirculation (EGR) rates while maintaining the high engine efficiency of the diesel process.
    4. 4
      Jeske, K.; Kizilkaya, A. C.; López-Luque, I.; Pfänder, N.; Bartsch, M.; Concepción, P.; Prieto, G. Design of Cobalt Fischer–Tropsch Catalysts for the Combined Production of Liquid Fuels and Olefin Chemicals from Hydrogen-Rich Syngas. ACS Catal. 2021, 11, 4784– 4798,  DOI: 10.1021/acscatal.0c05027
      4
      Design of Cobalt Fischer-Tropsch Catalysts for the Combined Production of Liquid Fuels and Olefin Chemicals from Hydrogen-Rich Syngas
      Jeske, Kai; Kizilkaya, Ali Can; Lopez-Luque, Ivan; Pfaender, Norbert; Bartsch, Mathias; Concepcion, Patricia; Prieto, Gonzalo
      ACS Catalysis (2021), 11 (8), 4784-4798CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      Adjusting hydrocarbon product distributions in the Fischer-Tropsch (FT) synthesis is of notable significance in the context of so-called X-to-liqs. (XTL) technologies. While cobalt catalysts are selective to long-chain paraffin precursors for synthetic jet- and diesel-fuels, lighter (C10-) alkane condensates are less valuable for fuel prodn. Alternatively, iron carbide-based catalysts are suitable for the coprodn. of paraffinic waxes alongside liq. (and gaseous) olefin chems.; however, their activity for the water-gas-shift reaction (WGSR) is notoriously detrimental when hydrogen-rich syngas feeds, for example, derived from (unconventional) natural gas, are to be converted. Herein the roles of pore architecture and oxide promoters of Lewis basic character on CoRu/Al2O3 FT catalysts are systematically addressed, targeting the development of catalysts with unusually high selectivity to liq. olefins. Both alkali and lanthanide oxides lead to a decrease in turnover frequency. The latter, particularly PrOx, prove effective to boost the selectivity to liq. (C5-10) olefins without undesired WGSR activity. In situ CO-FTIR spectroscopy suggests a dual promotion via both electronic modification of surface Co sites and the inhibition of Lewis acidity on the support, which has direct implications for double-bond isomerization reactivity and thus the regioisomery of liq. olefin products. D. functional theory calcns. ascribe oxide promotion to an enhanced competitive adsorption of mol. CO vs. hydrogen and olefins on oxide-decorated cobalt surfaces, dampening (secondary) olefin hydrogenation, and suggest an exacerbated metal surface carbophilicity to underlie the undesired induction of WGSR activity by strongly electron-donating alkali oxide promoters. Enhanced pore mol. transport within a multimodal meso-macroporous architecture in combination with PrOx as promoter, at an optimal surface loading of 1 Prat nm-2, results in an unconventional product distribution, reconciling benefits intrinsic to Co- and Fe-based FT catalysts, resp. A chain-growth probability of 0.75, and thus >70 C% selectivity to C5+ products, is achieved alongside lighter hydrocarbon (C5-10) condensates that are significantly enriched in added-value chems. (67 C%), predominantly α-olefins but also linear alcs., remarkably with essentially no CO2 side-prodn. (<1%). Such unusual product distributions, integrating precursors for synthetic fuels and liq. platform chems., might be desired to diversify the scope and improve the economics of small-scale gas- and biomass-to-liq. processes.
    5. 5
      Hellier, P.; Talibi, M.; Eveleigh, A.; Ladommatos, N. An Overview of the Effects of Fuel Molecular Structure on the Combustion and Emissions Characteristics of Compression Ignition Engines. Proc. Inst. Mech. Eng., Part D 2018, 232, 90– 105,  DOI: 10.1177/0954407016687453
      5
      An overview of the effects of fuel molecular structure on the combustion and emissions characteristics of compression ignition engines
      Hellier, Paul; Talibi, Midhat; Eveleigh, Aaron; Ladommatos, Nicos
      Proceedings of the Institution of Mechanical Engineers, Part D: Journal of Automobile Engineering (2018), 232 (1), 90-105CODEN: PMDEEA; ISSN:0954-4070. (Sage Publications Ltd.)
      Future fuels for compression ignition engines will be required both to reduce the anthropogenic carbon dioxide emissions from fossil sources and to contribute to the redns. in the exhaust levels of pollutants, such as nitrogen oxides and particulate matter. Via various processes of biol., chem. and phys. conversion, feedstocks such as lignocellulosic biomass and photosynthetic micro-organisms will yield a wide variety of potential fuel mols. Furthermore, modification of the prodn. processes may allow the targeted manuf. of fuels of specific mol. structure. This paper therefore presents an overview of the effects of fuel mol. structure on the combustion and emissions characteristics of compression ignition engines, highlighting in particular the submol. features common to a variety of potential fuels. An increase in the straight-chain length of the alkyl moiety reduces the duration of ignition delay, and the introduction of double bonds or branching to an alkyl moiety both increase ignition delay. The movement of a double bond towards the center of an alkyl chain, or the addn. of oxygen to a mol., can both increase and decrease the duration of ignition delay dependent on the overall fuel structure. Nitrogen oxide emissions are primarily influenced by the duration of fuel ignition delay, but in the case of hydrogen and methane pilot-ignited premixed combustion arise only at flame temps. sufficiently high for thermal prodn. An increase in arom. ring no. and phys. properties such as the fuel b.p. increase particulate matter emissions at const. combustion phasing.
    6. 6
      Choudhury, H. A.; Intikhab, S.; Kalakul, S.; Khan, M.; Tafreshi, R.; Gani, R.; Elbashir, N. O. Designing a Surrogate Fuel for Gas-to-Liquid Derived Diesel. Energy Fuels 2017, 31, 11266– 11279,  DOI: 10.1021/acs.energyfuels.7b00274
      6
      Designing a Surrogate Fuel for Gas-to-Liquid Derived Diesel
      Choudhury, H. A.; Intikhab, S.; Kalakul, S.; Khan, M.; Tafreshi, R.; Gani, R.; Elbashir, N. O.
      Energy & Fuels (2017), 31 (10), 11266-11279CODEN: ENFUEM; ISSN:0887-0624. (American Chemical Society)
      Synthetic diesel fuel produced from natural gas via gas-to-liq. (GTL) technol. is referred to as ultraclean fuel but is still challenged for full certification as diesel fuel. GTL diesel lacks certain hydrocarbons and chem. constituents, which although are benign to the environment, result in a trade-off in performance when used in a diesel engine. To boost GTL diesel physicochem. properties and thereby enable its use in conventional diesel engines, GTL diesel needs improvement. This can be achieved by mixing suitable additives to the GTL diesel and through the development of surrogate fuels that have fewer components. Screening of thousands of additives is a tedious task and can be done efficiently via computer based modeling to quickly and reliably identify a small no. of promising candidates. These models are used to guide the formulation of five surrogates and predict their physicochem. properties. These surrogates are further verified using rigorous math. tools as well as through advanced exptl. techniques. An optimal surrogate MI-5 is identified, which closely mimics GTL diesel-conventional diesel blends in terms of its physicochem. properties. An engine study for the surrogate is also performed to understand the effect of physicochem. properties on combustion as well as the emission behavior of the fuel. MI-5 exhibited an optimal torque at higher load conditions. A redn. of 11.26% NOx emission for MI-5 is obsd. when compared to conventional fuel. At higher loads, diesel fuel surpasses the total hydrocarbon (THC) emissions for both the surrogate and the GTL fuel. No significant variation in CO and CO2 emissions for MI-5, GTL diesel and conventional diesel is obsd. Anal. of combustion as well as emission behavior of the fuels helps to understand the role of physicochem. properties on the performance of the fuel.
    7. 7
      Graziano, B.; Schönfeld, S.; Heuser, B.; Pelerin, D. 1-Octanol as CO2-Neutral Fuel for Commercial Vehicle Applications. ATZheavy Duty Worldwide 2020, 13, 36– 41,  DOI: 10.1007/s35746-020-0114-7
      There is no corresponding record for this reference.
    8. 8
      Kohlpaintner, C.; Schulte, M.; Falbe, J.; Lappe, P.; Weber, J.; Frey, G. D. Aldehydes, Aliphatic. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, Germany, 2013.
      There is no corresponding record for this reference.
    9. 9
      Püschel, S.; Störtte, S.; Topphoff, J.; Vorholt, A. J.; Leitner, W. Green Process Design for Reductive Hydroformylation of Renewable Olefin Cuts for Drop-in Diesel Fuels. ChemSusChem 2021, 14, 5226– 5234,  DOI: 10.1002/cssc.202100929
      9
      Green Process Design for Reductive Hydroformylation of Renewable Olefin Cuts for Drop-In Diesel Fuels
      Pueschel, Sebastian; Stortte, Sven; Topphoff, Johanna; Vorholt, Andreas J.; Leitner, Walter
      ChemSusChem (2021), 14 (23), 5226-5234CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      CO2-neutral fuels are a way to cleaner and more sustainable mobility. Utilization of bio-syngas via Fischer-Tropsch (FT) synthesis represents an interesting route for the prodn. of tailormade biofuels. Recent developments in FT catalyst research led to olefin-enriched products, enabling the synthesis of alc.-enriched fuels by reductive hydroformylation of the C=C bond. Several alcs. have already proven to be suitable fuel additives with favorable combustion behavior. Here, a hydroformylation-hydrogenation sequence of FT-olefin-paraffin mixts. was investigated as a potential route to alcs. A liq.-liq. biphasic system with a rhodium/3,3',3''-phosphanetriyltris(benzenesulfonic acid) trisodium salt (TPPTS) catalyst system was chosen for effective catalyst recycling. After optimizing reaction conditions with a model substrate consisting of 1-octene and n-heptane the conversion of an actual olefin-contg. C5-C10 FT product fraction to alcs. in continuously operated processes for 37 h was achieved with a total turnover no. of 23679.
    10. 10
      Anastas, P.; Eghbali, N. Green Chemistry: Principles and Practice. Chem. Soc. Rev. 2010, 39, 301– 312,  DOI: 10.1039/b918763b
      10
      Green Chemistry: Principles and Practice
      Anastas, Paul; Eghbali, Nicolas
      Chemical Society Reviews (2010), 39 (1), 301-312CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Green Chem. is a relatively new emerging field that strives to work at the mol. level to achieve sustainability. The field has received widespread interest in the past decade due to its ability to harness chem. innovation to meet environmental and economic goals simultaneously. Green Chem. has a framework of a cohesive set of Twelve Principles, which have been systematically surveyed in this crit. review. This article covers the concepts of design and the scientific philosophy of Green Chem. with a set of illustrative examples. Future trends in Green Chem. are discussed with the challenge of using the Principles as a cohesive design system (93 refs.).
    11. 11
      Fogg, D. E.; Dos Santos, E. N. Tandem Catalysis: A Taxonomy and Illustrative Review. Coord. Chem. Rev. 2004, 248, 2365– 2379,  DOI: 10.1016/j.ccr.2004.05.012
      11
      Tandem catalysis: a taxonomy and illustrative review
      Fogg, Deryn E.; dos Santos, Eduardo N.
      Coordination Chemistry Reviews (2004), 248 (21-24), 2365-2379CODEN: CCHRAM; ISSN:0010-8545. (Elsevier B.V.)
      A review. A scheme is advanced for the classification of 1-pot, coupled catalytic transformations, which distinguishes between 1-pot, domino/cascade, and tandem catalysis. The last of these is divided into three subclasses: orthogonal, auto-tandem, and assisted tandem catalysis. The proposed taxonomy, and the potential of tandem catalysis in org. synthesis, are illustrated with examples drawn from olefin metathesis and hydroformylation chem.
    12. 12
      Rodrigues, F. M. S.; Kucmierczyk, P. K.; Pineiro, M.; Jackstell, R.; Franke, R.; Pereira, M. M.; Beller, M. Dual Rh–Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols. ChemSusChem 2018, 11, 2310– 2314,  DOI: 10.1002/cssc.201800488
      12
      Dual Rh-Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols
      Rodrigues, Fabio M. S.; Kucmierczyk, Peter K.; Pineiro, Marta; Jackstell, Ralf; Franke, Robert; Pereira, Mariette M.; Beller, Matthias
      ChemSusChem (2018), 11 (14), 2310-2314CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      An active and selective dual catalytic system to promote domino hydroformylation-redn. reactions is described. Apart from terminal, di- and trisubstituted olefins, for the first time the less active internal C-C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3-dimethylbut-2-ene is converted into the corresponding n-alc. with high yield (90 %) as well as regio- and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru-based Shvo's complex. A variety of arom. and aliph. alkenes can be directly used to obtain mainly linear alcs.
    13. 13
      Takahashi, K.; Yamashita, M.; Ichihara, T.; Nakano, K.; Nozaki, K. High-Yielding Tandem Hydroformylation/Hydrogenation of a Terminal Olefin to Produce a Linear Alcohol Using a Rh/Ru Dual Catalyst System. Angew. Chem., Int. Ed. 2010, 49, 4488– 4490,  DOI: 10.1002/anie.201001327
      13
      High-yielding tandem hydroformylation/hydrogenation of a terminal olefin to produce a linear alcohol using a Rh/Ru dual catalyst system
      Takahashi, Kohei; Yamashita, Makoto; Ichihara, Takeo; Nakano, Koji; Nozaki, Kyoko
      Angewandte Chemie, International Edition (2010), 49 (26), 4488-4490, S4488/1-S4488/12CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      1-Decene undergoes highly regio- and chemoselective tandem hydroformylation-redn. by use of binuclear ruthenium hydrido- and hydrogen bond-bridged tetraphenylcyclopentadienone-hydroxycyclopentadienyl complex (Shvo's catalyst) as a hydrogenation catalyst and rhodium acetylacetonate-Xantphos hydroformylation catalyst in a one-pot reaction. The optimized yields of 1-undecanol reached 90% with n/i ratio of 22 and aldehyde content of 1%.
    14. 14
      Diebolt, O.; Müller, C.; Vogt, D. “On-Water” Rhodium-Catalysed Hydroformylation for the Production of Linear Alcohols. Catal. Sci. Technol. 2012, 2, 773– 777,  DOI: 10.1039/c2cy00450j
      14
      "On-water" rhodium-catalysed hydroformylation for the production of linear alcohols
      Diebolt, Olivier; Mueller, Christian; Vogt, Dieter
      Catalysis Science & Technology (2012), 2 (4), 773-777CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      Optimization of the reaction conditions for the rhodium-catalyzed aldehyde hydrogenation under hydroformylation conditions showed that water used as co-solvent enhances both rate and selectivity towards primary alcs. One-pot hydroformylation-hydrogenation using rhodium as the only transition metal yielded alcs. in excellent selectivities and good linearities.
    15. 15
      van Winkle, J. L.; Lorenzo, S.; Morris, R. C.; Mason, R. F. Single Stage Hydroformylation of Olefins to Alcohols. U.S. Patent US3420898A1969.
      There is no corresponding record for this reference.
    16. 16
      Slaugh, L. H.; Mullineaux, R. D. Hydroformylation of Olefins. U.S. Patent US3239569A1966.
      There is no corresponding record for this reference.
    17. 17
      Fuchs, S.; Lichte, D.; Dittmar, M.; Meier, G.; Strutz, H.; Behr, A.; Vorholt, A. J. Tertiary Amines as Ligands in a Four-Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers. ChemCatChem 2017, 9, 1436– 1441,  DOI: 10.1002/cctc.201601518
      17
      Tertiary Amines as Ligands in a Four-Step Tandem Reaction of Hydroformylation and Hydrogenation: An Alternative Route to Industrial Diol Monomers
      Fuchs, Sarah; Lichte, Dominik; Dittmar, Morten; Meier, Gregor; Strutz, Heinz; Behr, Arno; Vorholt, Andreas J.
      ChemCatChem (2017), 9 (8), 1436-1441CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A catalyst system [dirhodium tetraoctanoate (Rh2(oct)4) and Et3N in toluene] is developed for the chemoselective tandem hydroformylation and hydrogenation of dicyclopentadiene under 70 bar H2 and CO at 120° to yield tricyclodecanedimethanols; under optimized conditions, a 79% yield of diols was obtained without the formation of olefin hydrogenation byproducts. 1,3-Divinylbenzene and 5-vinyl-2-norbornene yielded the corresponding dimethanols under similar conditions with 8 and 60% of aldol side products formed, resp.; tandem hydroformylation and hydrogenation of 4-vinylcyclohexene and norbornadiene yielded aldol adducts as the major or exclusive products. The catalyst was recycled by water extn. of the product from the reaction mixt. and recycling of the toluene phase.
    18. 18
      Fuchs, S.; Lichte, D.; Jolmes, T.; Rösler, T.; Meier, G.; Strutz, H.; Behr, A.; Vorholt, A. J. Synthesis of Industrial Primary Diamines via Intermediate Diols – Combining Hydroformylation, Hydrogenation and Amination. ChemCatChem 2018, 10, 4126– 4133,  DOI: 10.1002/cctc.201800950
      18
      Synthesis of Industrial Primary Diamines via Intermediate Diols - Combining Hydroformylation, Hydrogenation and Amination
      Fuchs, Sarah; Lichte, Dominik; Jolmes, Tristan; Roesler, Thorsten; Meier, Gregor; Strutz, Heinz; Behr, Arno; J. Vorholt, Andreas
      ChemCatChem (2018), 10 (18), 4126-4133CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Dicyclopentadiene underwent hydrohydroxymethylation (via hydroformylation and hydrogenation) followed by amination with ammonia in the presence of combinations of dirhodium tetraoctanoate, RuHCl(CO)(PPh3)3, Xantphos, and Et3N in tert-amyl alc. to yield the tricyclodecanedimethanamine I (as a mixt. of its four regioisomers); the hydrohydroxymethylation and amination reactions were performed both in sequence and in tandem. High yields of both the hydrohydroxymethylation and amination reactions were obtained, but the presence of rhodium in the amination reaction or of ruthenium in the hydrohydroxymethylation reaction inhibits the reactions and worsens their selectivities. Using sequential hydrohydroxymethylation and amination reactions, I was obtained in 88% yield.
    19. 19
      Gorbunov, D.; Nenasheva, M.; Naranov, E.; Maximov, A.; Rosenberg, E.; Karakhanov, E. Tandem Hydroformylation/Hydrogenation over Novel Immobilized Rh-Containing Catalysts Based on Tertiary Amine-Functionalized Hybrid Inorganic-Organic Materials. Appl. Catal., A 2021, 623, 118266  DOI: 10.1016/j.apcata.2021.118266
      19
      Tandem hydroformylation/hydrogenation over novel immobilized Rh-containing catalysts based on tertiary amine-functionalized hybrid inorganic-organic materials
      Gorbunov, Dmitry; Nenasheva, Maria; Naranov, Evgeny; Maximov, Anton; Rosenberg, Edward; Karakhanov, Eduard
      Applied Catalysis, A: General (2021), 623 (), 118266CODEN: ACAGE4; ISSN:0926-860X. (Elsevier B.V.)
      Non-phosphorous rhodium-contg. catalysts for direct conversion of olefins to alcs. via tandem hydroformylation/hydrogenation have been designed and synthesized. Interaction between Rh(acac)(CO)2 and tertiary amino groups on the surface of mesoporous hybrid org.-inorg. supports yielded materials which were successfully used in the tandem process. Data obtained for a selected catalyst KN demonstrate that rhodium is in the Rh+1 state highly dispersed on the surface and is bonded with nitrogen atoms both before and after use. Evaluation of the catalytic performance shows high activity (hydroformylation TOF 312 h-1), chemoselectivity and stable hydroformylation yield at least in the first 5 cycles with a decrease in alc. selectivity. The influence of temp., reaction time, total pressure, and molar CO/H2 ratio of syngas on oxygenate yields is described. Type of the hydroformylation active sites and possible pathways for the obsd. decrease in hydrogenation are discussed.
    20. 20
      Furst, M. R. L.; Korkmaz, V.; Gaide, T.; Seidensticker, T.; Behr, A.; Vorholt, A. J. Tandem Reductive Hydroformylation of Castor Oil Derived Substrates and Catalyst Recycling by Selective Product Crystallization. ChemCatChem 2017, 9, 4319– 4323,  DOI: 10.1002/cctc.201700965
      20
      Tandem Reductive Hydroformylation of Castor Oil Derived Substrates and Catalyst Recycling by Selective Product Crystallization
      Furst, Marc R. L.; Korkmaz, Vedat; Gaide, Tom; Seidensticker, Thomas; Behr, Arno; Vorholt, Andreas J.
      ChemCatChem (2017), 9 (23), 4319-4323CODEN: CHEMK3; ISSN:1867-3880. (Wiley-VCH Verlag GmbH & Co. KGaA)
      An orthogonal tandem catalytic system consisting of rhodium and ruthenium complexes yielded linear C12 α,ω-bifunctional compds. from com., castor oil derived renewable substrates. With aldehyde yields up to 88 % and selectivities to the linear species of up to 95 %, this approach is direct and atom economic and provides easy access to potential polymer precursors for polycondensates. Addnl., a straightforward method for selective product crystn. was developed, which enabled recycling of the tandem catalytic system for two runs with excellent activity and simultaneously provided a high-purity product.
    21. 21
      Rösler, T.; Ehmann, K. R.; Köhnke, K.; Leutzsch, M.; Wessel, N.; Vorholt, A. J.; Leitner, W. Reductive Hydroformylation With A Selective And Highly Active Rhodium Amine System. J. Catal. 2021, 400, 234– 243,  DOI: 10.1016/j.jcat.2021.06.001
      There is no corresponding record for this reference.
    22. 22
      Cheung, L. L. W.; Vasapollo, G.; Alper, H. Synthesis of Alcohols via a Rhodium-Catalyzed Hydroformylation-Reduction Sequence Using Tertiary Bidentate Amine Ligands. Adv. Synth. Catal. 2012, 354, 2019– 2022,  DOI: 10.1002/adsc.201200053
      22
      Synthesis of Alcohols via a Rhodium-Catalyzed Hydroformylation - Reduction Sequence using Tertiary Bidentate Amine Ligands
      Cheung, Lawrence L. W.; Vasapollo, Giuseppe; Alper, Howard
      Advanced Synthesis & Catalysis (2012), 354 (10), 2019-2022, S2019/1-S2019/16CODEN: ASCAF7; ISSN:1615-4150. (Wiley-VCH Verlag GmbH & Co. KGaA)
      The synthesis of alcs. from arom. olefins is described using a rhodium-catalyzed hydroformylation-redn. sequence with the assistance of a tertiary diamine ligand. The alcs., e.g., I (R = H, Me, MeO, Ph, Cl), are produced in excellent branched to linear ratios and in good to excellent isolated yields. In all cases no aldehyde product, from hydroformylation, or alkyl product, from olefin redn., was detected.
    23. 23
      Vanbésien, T.; Monflier, E.; Hapiot, F. Rhodium-Catalyzed One Pot Synthesis of Hydroxymethylated Triglycerides. Green Chem. 2016, 18, 6687– 6694,  DOI: 10.1039/c6gc02706g
      23
      Rhodium-catalyzed one pot synthesis of hydroxymethylated triglycerides
      Vanbesien, T.; Monflier, E.; Hapiot, F.
      Green Chemistry (2016), 18 (24), 6687-6694CODEN: GRCHFJ; ISSN:1463-9262. (Royal Society of Chemistry)
      The direct functionalization of the carbon-carbon double bonds of triglycerides is of major interest to access biosourced building blocks with unique mol. and functional properties. In this study, we described the synthesis of trihydroxylated triglycerides via a hydrohydroxymethylation reaction, which consists of two consecutive Rh-catalyzed reactions, namely, a hydroformylation followed by a consecutive redn. of formyl groups. Contrary to two-step procedures described in the literature, no phosphane was used to coordinate Rh-species, thus giving our strategy an industrial potential. Tertiary amines were used as ligands to promote the hydrohydroxymethylation reaction. The Rh/amine-catalyst proved to be active both in hydroformylation of the carbon-carbon double bond and redn. of the resulting aldehyde into alc. The proportion of hydroxyl groups grafted onto triglyceride fatty chains was optimized by a careful choice of exptl. conditions, esp. the nature and the amt. of the tertiary amine, the reaction temp., and the CO/H2 pressure.
    24. 24
      Ternel, J.; Lopes, A.; Sauthier, M.; Buffe, C.; Wiatz, V.; Bricout, H.; Tilloy, S.; Monflier, E. Reductive Hydroformylation of Isosorbide Diallyl Ether. Molecules 2021, 26, 7322  DOI: 10.3390/molecules26237322
      24
      Reductive Hydroformylation of Isosorbide Diallyl Ether
      Ternel, Jeremy; Lopes, Adrien; Sauthier, Mathieu; Buffe, Clothilde; Wiatz, Vincent; Bricout, Herve; Tilloy, Sebastien; Monflier, Eric
      Molecules (2021), 26 (23), 7322CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
      Herein, hydroformylation of isosorbide diallyl ether using a rhodium/amine catalytic system has been studied. The highest yield of bis-primary alcs. obtained was equal to 79%.
    25. 25
      Püschel, S.; Hammami, E.; Ehmann, K. R.; Rösler, T.; Leitner, W.; Vorholt, A. J. Auto-Tandem Catalytic Reductive Hydroformylation with Continuous Multiphase Catalyst Recycling. Catal. Sci. Technol. 2022, 12, 728– 736,  DOI: 10.1039/D1CY02000E
      25
      Auto-tandem catalytic reductive hydroformylation with continuous multiphase catalyst recycling
      Pueschel, Sebastian; Hammami, Enes; Roesler, Thorsten; Ehmann, Kira R.; Vorholt, Andreas J.; Leitner, Walter
      Catalysis Science & Technology (2022), 12 (3), 728-736CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      The prodn. of alcs. from olefin-enriched Fischer-Tropsch products represents a promising route for CO2-neutral bio-synthetic fuels. Tandem-catalytic systems as alternatives for the conventional two-step prodn. of long-chain alcs. are attractive in terms of energy and resource efficiency. Herein, we present the first rhodium-based catalytic system capable of direct conversion of olefins to alcs. in a biphasic liq./liq. system. After optimizing the reaction conditions for the biphasic operation, an alc. selectivity of up to 64% was achieved, while aldehydes and olefin isomers were obsd. as main byproducts. By employing water-sol. alkanolamines, the catalyst is immobilized in a water phase and can be easily sepd. from the product contg. an org. phase with a rhodium loss of as low as 0.1%. After investigation of various reaction parameters, a TON of 128 in batch operation was achieved. Furthermore, the developed catalyst recycling strategy was implemented in a continuously operated miniplant, reaching a TTON for alc. prodn. of 1236 after 50 h.
    26. 26
      Großeheilmann, J.; Vanderveen, J. R.; Jessop, P. G.; Kragl, U. Switchable-Hydrophilicity Solvents for Product Isolation and Catalyst Recycling in Organocatalysis. ChemSusChem 2016, 9, 696– 702,  DOI: 10.1002/cssc.201501654
      26
      Switchable-Hydrophilicity Solvents for Product Isolation and Catalyst Recycling in Organocatalysis
      Grosseheilmann, Julia; Vanderveen, Jesse R.; Jessop, Philip G.; Kragl, Udo
      ChemSusChem (2016), 9 (7), 696-702CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Switchable-hydrophilicity solvents (SHSs) are solvents that can switch reversibly between a water-miscible state to a state that forms a biphasic mixt. with water. In this case study, SHSs have been studied for easy product/catalyst sepn. as well as catalyst recycling. A series of tertiary amine SHSs have been identified for the extn. of the hydrophilic product from the postreaction mixt. Here, the authors detd. high extn. efficiencies for the product (>84%) and low extn. rates for the catalyst (<0.1%). With the catalyst recycling expts., we isolated the product in high purity (>98%) without further purifn. steps. At the same time, the catalyst was reused without any loss of activity (>91% enantiomeric excess, >99% yield) four times. Furthermore, the authors optimized the extn. efficiency by working with a microextractor. In addn., with the use of a falling-film microreactor, the authors obtained the product with high enantioselectivity by working at ambient conditions.
    27. 27
      Jessop, P. G.; Mercer, S. M.; Heldebrant, D. J. CO2-Triggered Switchable Solvents, Surfactants, and Other Materials. Energy Environ. Sci. 2012, 5, 7240– 7253,  DOI: 10.1039/c2ee02912j
      27
      CO2-triggered switchable solvents, surfactants, and other materials
      Jessop, Philip G.; Mercer, Sean M.; Heldebrant, David J.
      Energy & Environmental Science (2012), 5 (6), 7240-7253CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      A review. Waste CO2 at atm. pressure can be used to trigger dramatic changes in the properties of certain switchable materials. Compared to other triggers such as light, acids and oxidants, CO2 has the advantages that it is inexpensive, nonhazardous, non-accumulating in the system, easily removed, and it does not require the material to be transparent. Known CO2-triggered switchable materials now include solvents, surfactants, solutes, catalysts, particles, polymers, and gels. These have also been described as "smart" materials or, for some of the switchable solvents, "reversible ionic liqs.". The added flexibility of switchable materials represents a new strategy for minimizing energy and material consumption in process and product design.
    28. 28
      Alshamrani, A. K.; Vanderveen, J. R.; Jessop, P. G. A Guide to the Selection of Switchable Functional Groups for CO2-Switchable Compounds. Phys. Chem. Chem. Phys. 2016, 18, 19276– 19288,  DOI: 10.1039/c6cp03302d
      28
      A guide to the selection of switchable functional groups for CO2-switchable compounds
      Alshamrani, A. K.; Vanderveen, J. R.; Jessop, P. G.
      Physical Chemistry Chemical Physics (2016), 18 (28), 19276-19288CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Many CO2-responsive species, including many of the CO2-switchable surfactants, solvents, solutes, gels, colloids, and surfaces, rely on the ability of CO2 to lower the pH of water. Uncharged basic groups on the CO2-responsive species are therefore converted from a neutral state to a protonated cationic state (a bicarbonate salt), which causes dramatic and useful changes to the properties of the species. However, this switching process only works correctly if a basic group of appropriate basicity has been selected. This article presents a comprehensive guide to the selection of basic groups for CO2-switchable species for use in water. The appropriate basicity, as measured by the pKaH (the pKa of the protonated compd.), is a function of the concn. of the switchable species, the temp., the pressure of CO2, the presence or absence of an org. liq. phase, and the soly. of the neutral form of the compd.
    29. 29
      Mercer, S. M.; Robert, T.; Dixon, D. V.; Jessop, P. G. Recycling of a Homogeneous Catalyst Using Switchable Water. Catal. Sci. Technol. 2012, 2, 1315– 1318,  DOI: 10.1039/c2cy20095c
      29
      Recycling of a homogeneous catalyst using switchable water
      Mercer, Sean M.; Robert, Tobias; Dixon, Daniel V.; Jessop, Philip G.
      Catalysis Science & Technology (2012), 2 (7), 1315-1318CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      Aq./org. biphasic catalysis allows easy sepn. of a homogeneous catalyst from product, but is often inefficient when hydrophobic substrates are used. A system based on switchable water is monophasic in the absence of CO2 and biphasic in its presence. Catalysis can be performed in the monophasic solvent, and then switched to a biphasic system, sepg. catalyst from product. Removal of CO2 allows for easy recycling of the catalyst. Hydroformylations have been achieved using this solvent system. The catalyst was recycled several times with minimal loss of activity.
    30. 30
      Künnemann, K. U.; Bianga, J.; Scheel, R.; Seidensticker, T.; Dreimann, J. M.; Vogt, D. Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System. Org. Process Res. Dev. 2020, 24, 41– 49,  DOI: 10.1021/acs.oprd.9b00409
      30
      Process Development for the Rhodium-Catalyzed Reductive Amination in a Thermomorphic Multiphase System
      Kuennemann, Kai U.; Bianga, Jonas; Scheel, Ricarda; Seidensticker, Thomas; Dreimann, Jens M.; Vogt, Dieter
      Organic Process Research & Development (2020), 24 (1), 41-49CODEN: OPRDFK; ISSN:1083-6160. (American Chemical Society)
      For the first time, the successful application of the homogeneously catalyzed reductive amination in a thermomorphic multiphase system (TMS) and the first reported scale-up of this reaction into a continuous process, which recovers and recycles the homogeneous catalyst in flow, is presented. Herein, the model substrate 1-decanal reacts with the secondary amine diethylamine to form the corresponding product N,N-diethyldecylamine. A thermomorphic multiphase system (TMS) is established as a recycling strategy to recover and reuse the catalyst for the continuous process. After screening different solvents for the TMS and optimizing the reaction conditions in batch mode, the recycling of the rhodium catalyst was realized in a fully automated miniplant. Parameters influencing the stability of the process were identified and optimized to develop the continuous process. The process was operated in a steady state over 90 h with yields >90% of the desired product and low catalyst leaching <1%/h.
    31. 31
      Cao, F.; Gao, H.; Li, H.; Liang, Z. Experimental and Theoretical Studies on Mass Transfer Performance for CO 2 Absorption into Aqueous N, N -Dimethylethanolamine Solution in the Polytetrafluoroethylene Hollow-Fiber Membrane Contactor. Ind. Eng. Chem. Res. 2018, 57, 16862– 16874,  DOI: 10.1021/acs.iecr.8b02901
      31
      Experimental and Theoretical Studies on Mass Transfer Performance for CO2 Absorption into Aqueous N,N-Dimethylethanolamine Solution in the Polytetrafluoroethylene Hollow-Fiber Membrane Contactor
      Cao, Fan; Gao, Hongxia; Li, Haipeng; Liang, Zhiwu
      Industrial & Engineering Chemistry Research (2018), 57 (49), 16862-16874CODEN: IECRED; ISSN:0888-5885. (American Chemical Society)
      N,N-Dimethylethanolamine (DMEA) is a promising absorbent due to the relative higher reaction rate and high capacity for CO2 capture. In this work, the CO2 absorption performance into aq. DMEA soln. using a polytetrafluoroethylene (PTFE) hollow-fiber membrane contactor (HFMC) was investigated exptl. and numerically. The CO2 absorption fluxes were detd. under various important operating parameters, including liq. velocity, gas velocity, liq. feed temp., CO2 partial pressure, and CO2 loading in liq. phase. In addn., a 2D steady-state math. model was established to predict the CO2 absorption flux in two operation modes, non-wetted and partially wetted modes, and was validated by using the CO2 absorption into water and aq. MEA soln. The exptl. and simulated results revealed that the CO2 absorption flux can be enhanced by increasing liq. velocity, liq.-phase temp., and amine concn. in a moderate range. Also, the CO2 absorption flux will increase with the increasing gas velocity and CO2 partial pressure but decrease with increasing CO2 loading in the liq. phase. In addn., the membrane wetting can cause a severe deterioration in the CO2 absorption performance even with a slight membrane wetting. The CO2 absorption fluxes for CO2 absorption into DMEA solns. show the good agreement with or are closer to the simulated data with the membrane wetting of 10% under the same operational conditions, with the av. abs. relative deviation (AARD) of 5.02%. Furthermore, the obtained radial and axial CO2 concn. profiles from the math. model were also discussed to further understand the CO2 absorption process.
    32. 32
      Purwanto, P.; Deshpande, R. M.; Chaudhari, R. V.; Delmas, H. Solubility of Hydrogen, Carbon Monoxide, and 1-Octene in Various Solvents and Solvent Mixtures. J. Chem. Eng. Data 1996, 41, 1414– 1417,  DOI: 10.1021/je960024e
      32
      Solubility of Hydrogen, Carbon Monoxide, and 1-Octene in Various Solvents and Solvent Mixtures
      Purwanto, P.; Deshpande, R. M.; Chaudhari, R. V.; Delmas, H.
      Journal of Chemical and Engineering Data (1996), 41 (6), 1414-1417CODEN: JCEAAX; ISSN:0021-9568. (American Chemical Society)
      The soly. of H2 has been measured as a function of pressure in ethanol + water and various solvents at (298 and 323) K. The results are compared with theor. predictions for H2 in different solvents and some mixts. and found to agree within ±10% error, except for acetonitrile. The soly. of CO in 1-octene has also been measured. Liq.-liq. equil. for the 1-octene + water + ethanol system was measured at (298 and 323) K, but the predictions of these data by the UNIFAC-UNIQUAC models were not found to be satisfactory, except for higher 1-octene concns. in water (>6% wt./wt.) for which the predictions were within 10% error.
    33. 33
      Torres, G. M.; Frauenlob, R.; Franke, R.; Börner, A. Production of Alcohols via Hydroformylation. Catal. Sci. Technol. 2015, 5, 34– 54,  DOI: 10.1039/c4cy01131g
      33
      Production of alcohols via hydroformylation
      Torres, Galina Morales; Frauenlob, Robin; Franke, Robert; Boerner, Armin
      Catalysis Science & Technology (2015), 5 (1), 34-54CODEN: CSTAGD; ISSN:2044-4753. (Royal Society of Chemistry)
      A review. The numerous approaches for the catalytic synthesis of alkyl alcs. using an intermediate hydroformylation step are reviewed. One main strategy is a sequence where hydroformylation and hydrogenation are carried out step by step. More challenging are hydroformylation reactions under reducing conditions. In this regard, the transformation can be assisted by two different catalysts or one single catalyst (tandem reaction). A particular challenge in this respect is the undesired olefin hydrogenation. Sequences where hydroformylation is combined with a subsequent aldol reaction are of huge economic importance. The different performances of the catalytic systems on the basis of rhodium, cobalt, palladium, and ruthenium are described together with typical org. ligands, reaction conditions, and selected applications.
    34. 34
      Becquet, C.; Berche, F.; Bricout, H.; Monflier, E.; Tilloy, S. Hydrohydroxymethylation of Ethyl Ricinoleate and Castor Oil. ACS Sustainable Chem. Eng. 2021, 9, 9444– 9454,  DOI: 10.1021/acssuschemeng.1c02924
      34
      Hydrohydroxymethylation of Ethyl Ricinoleate and Castor Oil
      Becquet, Chryslain; Berche, Francois; Bricout, Herve; Monflier, Eric; Tilloy, Sebastien
      ACS Sustainable Chemistry & Engineering (2021), 9 (28), 9444-9454CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
      The direct functionalization of the carbon-carbon double bonds of castor oil and its derivs. is of major interest to access biosourced building blocks. In particular, polyol derivs. can be produced in this way and find application in the field of bio-based polyesters and polyurethanes. In this study, we described the synthesis of polyhydroxylated derivs. via a hydrohydroxymethylation reaction consisting of two consecutive Rh-catalyzed reactions: a hydroformylation reaction followed by a hydrogenation reaction of formyl groups. A catalytic system based on Rh(acac)(CO)2 and a trialkylamine proved to be active both in hydroformylation of carbon-carbon double bonds and redn. of the resulting aldehydes into primary alcs. By optimizing the reaction conditions, yields in alcs. of 74 and 80% were reached for castor oil and Et ricinoleate, resp.
    35. 35
      Nenasheva, M.; Gorbunov, D.; Karasaeva, M.; Maximov, A.; Karakhanov, E. Non-Phosphorus Recyclable Rh / Triethanolamine Catalytic System for Tandem Hydroformylation / Hydrogenation and Hydroaminomethylation of Olefins under Biphasic Conditions. Mol. Catal. 2021, 516, 112010  DOI: 10.1016/j.mcat.2021.112010
      35
      Non-phosphorus recyclable Rh/triethanolamine catalytic system for tandem hydroformylation/hydrogenation and hydroaminomethylation of olefins under biphasic conditions
      Nenasheva, Maria; Gorbunov, Dmitry; Karasaeva, Moldir; Maximov, Anton; Karakhanov, Eduard
      Molecular Catalysis (2021), 516 (), 112010CODEN: MCOADH ISSN:. (Elsevier B.V.)
      For the first time, one-pot hydroformylation/hydrogenation and hydroaminomethylation of olefins are performed under biphasic conditions using a non-phosphorous Rh/amine catalytic system. Available, cheap, and non-toxic triethanolamine was found to be an effective water-sol. ligand, providing easy sepn. and reuses of the catalytic system without significant loss in activity.

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    • Detailed experimental protocol and information on the used equipment, additional information on the phase behavior simulation, and IR spectra of CO2 loaded and regenerated reaction mixture (PDF)


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