This article summarizes a steam reforming case study focusing on catalyst development for hydrogen production from glycerol and methane. It integrates insights from Avantium’s high throughput testing capabilities and the customer project with Avantium.

Project Background

Our customer is transitioning into biobased products using syngas derived from biomaterials such as glycerin. The project aims to identify catalysts capable of converting glycerin at 500°C with minimal methane conversion, low coke formation, long catalyst life, and short residence time.

Objectives

• Evaluate five catalyst candidates for glycerin steam reforming.
• Optimize for hydrogen yield, catalyst longevity, and operational efficiency.
• Ensure low pressure drop and stable reactor performance.

Flowrence® High Throughput Reactor System

The catalyst testing for this project was conducted using Avantium’s proprietary Flowrence® Technology, a high-throughput micro-pilot plant platform designed for parallel catalyst testing. It ensures unmatched reactor-to-reactor repeatability and high data quality.

• Reactor Configuration: 64 parallel reactors (4 blocks × 16 reactors)
• Reactor Type: Quartz tube reactors with alpha alumina as inert diluent were selected after validation for their stability and no pressure drop under reforming conditions.
• Reactor Loading: Single-Pellet-String Reactor (SPSR) design ensures uniform catalyst packing and minimal catalyst usage.
• Feed Distribution: Microfluidics and Active Liquid Distribution (ALD) ensure precise and uniform feed delivery across all reactors.
• Pressure Control: Reactor pressure is individually controlled, enabling high-pressure operation with gas-phase feeds.
• Flexibility: Supports a wide range of chemistries including steam reforming, hydrogenation, oxidation.
• Data Management: Integrated with advanced data analytics tools for real-time monitoring and post-run analysis.

Advantages for the Project

• Enabled side-by-side testing of up to 64 catalyst variants under identical conditions.
• Delivered high-confidence data for hydrogen and CO₂ production, pressure stability, and catalyst deactivation trends.
• Allowed rapid iteration and optimization of catalyst formulations, including Ru, Pt, Pd, and Ni on various supports.

Avantium’s proprietary Flowrence® flexible testing platform was instrumental in accelerating the catalyst development timeline and ensuring reliable, reproducible results for our customer biobased hydrogen production goals.

Case Study: Steam Reforming of Glycerol and Methane

The catalyst testing program was structured into three major runs, each designed to refine catalyst selection and reactor configuration for optimal hydrogen production from glycerol and methane.

Validation Run

Test multiple configurations and different reactor types to identify the best setup for the subsequent tests. Various catalyst supports were tested in staineless steel and quartz reactors also to evaluate the effect on pressure drop.

• Setup: Quartz tube reactors with alpha alumina as diluent.
• Outcome: This configuration showed no pressure drop (ΔP) under reforming conditions with CH₄ and glycerol, making it the standard for subsequent tests.

Run 02: Coking Study

• System: 64 parallel nanoflow reactors (4 blocks × 16 reactors).
• Temperatures: 500°C, 575°C, 650°C, 725°C.
• Catalysts: 2 catalysts per block, 8 reactors each.
• Goal: Evaluate coking tendencies using a reference catalyst. Monitor pressure drop (ΔP) over 48 hours to assess catalyst stability.

Run 03: Catalyst Optimization

Catalyst Pool: 25 new catalysts developed to reduce Ru loading.

Feed Conditions:

• CH₄ only
• CH₄ + 42% glycerol + 0.5 mol% O₂
• CH₄ + 42% glycerol

Metals Tested: Ru, Pt, Pd, Ni.

Supports: HT and SC types.

Key Observations:

• Ru-based catalysts consistently outperformed the reference catalyst at 650°C for both CH₄ and CH₄ + glycerol feeds.
• Support material significantly influenced H₂ and CO₂ yields.
• No ΔP observed for successful catalysts at both 500°C and 650°C.
• Color variation in catalysts indicated differences in metal-support interactions and performance.