Kinetic modeling of homogeneous methanol synthesis catalyzed by base-promoted nickel complexes
Bibliographic record
Abstract
Nickel complexes promoted by alkoxide bases can affect facile conversion of synthesis gas into methanol under thermodynamically favorable temperatures. At 100°C, syngas conversion of 99% with turnover frequency of 66 h-1 is reported. The reaction is truly catalytic in Ni as well as in base. A kinetic study of the Ni(CO)4-KOMe catalyst system in 1,2-bis(2-methoxy ethoxy)ethane (triglyme)-MeOH solvent mixture is presented. The kinetic expression includes terms of zero-order in H2 and first-order in CO with syngas of H2-CO stoichiometry of ~2:1 and less than first-order in Ni (0.03-0.10 M), ~third-order in base (2.0-4.75 M), and an exponential dependence on methanol concentration (13.0-23.7 M at 2.0 M base; 15.8-22.6 M at 3.0 M base). The activation energy of 42.2 kJ mol-1 was estimated from the Arrhenius plot of the data between 374 and 393 K. Gas phase IR spectrum at the end of each run showed an intense signature peak at 2060 cm-1 for Ni(CO)4. Process uncertainties to commercialization of this versatile homogenous catalyst system for CO hydrogenation to methanol are discussed.Key words: homogeneous catalysis, syngas conversion, methanol synthesis, alkoxides, carbonyls of nickel.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.000 |
| Insufficient payload (model declined to judge) | 0.002 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".