Customer Case Study
A new catalyst for selective hydrogenation of an intermediate that achieves Customer’s SUSTAINABILITY GOALS
Objectives & Plan
Customer challenged ThruPore to develop a “more sustainable” heterogeneous catalyst for their current continuous process that makes a high-volume intermediate end-product. The fundamental sustainability catalyst challenges included:
- Produce fewer undesirable by-products;
- Reduce (ideally eliminate) the use of solvents in the process;
- Use (much) less precious metal in the catalyst;
- Lower the process costs.
ThruPore proposed a comprehensive new catalyst formulation and optimization plan for the customer, to be completed within 8 weeks. The Catalyst Development Project Plan is outlined below.
Step 1. Catalyst Screening
ThruPore scientists reviewed the relevant literature, used published conditions, to identify and select two off-the-shelf precious metal catalysts at certain wt-%-loadings as starting points. Additional metals for consideration included ruthenium and platinum. Results from these tests provided key indicators for adjusting activity vs. selectivity results. It was important to note that the combination of support structure, metal precursor/pretreatment, and the reaction pH play a vital role in the hydrogenation.
Step 2: Catalyst Reformulation
ThruPore scientists altered the surface chemistry of the synthetic carbon support, changed the precious metal precursor which was used, and adjusted the pH of the process reaction. Reformulation of this reaction was achieved in 10 reactions, which is at the higher end of the typical # of reactions for this step.
Step 3: Process Optimization
ThruPore scientists performed optimization that maximized conversion rate and enhanced selectivity of the desired end-product. The key variables included: temperature, pressure, substrate loading, and leveling reagent loadings to ideal stochiometric levels. Unwanted solvent in the reaction system was removed, yielding an optimized process under neat conditions. Certain pretreatments were considered and tested that increase activity (conversion rate). This step required 20 reactions, a lower # than typically found for this step.
Step 4: Lifetime / Reusability Studies
Catalyst lifetime and regeneration is a critical economic driver for process economics. ThruPore scientists verified that there was little precious metal leaching, and generated data indicating a lifetime metric of the new catalyst. The reusability study ran a total of 10 reactions, and included comparison tests with the existing commercial catalysts being used.
Results
A key reason for approaching ThruPore with this specific sustainability challenge was to dramatically reduce precious metal usage. ThruPore’s highly porous carbon support enables much less precious metal to be used. ThruPore’s synthetic carbon provides different dispersion characteristics and reaction kinetics, also requiring that screening occur for comparing results.
ThruPore completed the Development Project with 40 total reactions/experiments, which is much less than the 50 to 60 reactions a typical catalyst development project requires.
ThruPore’s new catalyst developed achieved the Company’s Sustainability Goals by accomplishing these new metrics:
- Reduced precious metal usage by 80%;
- Eliminated 100% of solvent in process;
- Increased reaction rate by 3x;
- Reduce by-products by 13%;
- More than doubled the lifetime (reducing downtime);
Next Steps
12 months – Pilot Project going through internal justification, and Pilot Testing to be performed at Customer’s facility (or at an outside pilot testing facility).
18 months – New catalyst full implementation will be performed with ThruPore Engineers assisting with onsite process tuning and servicing catalyst load as needed.
High Oleic Acid
Oleic acid is a desirable building block chemical due to its oxidative stability, reactivity potential and low pour point, making it attractive for use in paints, lubricants, and cosmetics. The downstream applications of oleic acid’s simple derivatives go beyond edible oils and biodiesel to include emulsifiers, polymer production, pharmaceuticals, and even paper recycling. The estimated value of the oleic acid market is $2.8 billion and is growing at >7% per year.
Currently, oleic acid is generated from genetically modified organisms (GMO’s) of canola or sunflowers. These GMO’s allow for >70% of the oil from these plants to be oleic acid, and the GMO’s of canola and sunflowers are quite expensive. Oleic acid trades at a significant premium to soybean oil, corn oil, and palm oil, as much as +50%. GMO’s of these lower value species have been created, but have only produced species capable of producing 75% oleic acid.
Below is relevant associated test data from the hydrogenation of ethyl linoleate:
|
Catalyst |
Reaction Conditions |
Conversion (%) |
Selectivity (%) |
|||
|
H2 (psi) |
Temp (oC) |
Time (hrs) |
Oleate (%) |
Stearate (%) |
||
| ThruPore |
14.7 |
60 |
3 |
99 |
92 |
7 |
| Competition |
14.7 |
60 |
3 |
14 |
3 |
11 |
What this data says is that at full conversion time – 3 hrs. – ThruPore’s catalyst delivered 92% of the desired end product, ethyl oleate. In comparison, a competitive catalyst showed only 14% conversion in the same timeframe, at a 3% – much less – yield of end product.