Decarbonisation Technology - May 2024 Issue

as a maritime fuel and may also be used for industrial transportation applications in rail and trucking operations. CO 2 capture is integral to ammonia production In many large-scale ammonia plants, hydrogen is produced using a two-stage reforming process. The primary reformer is generally an SMR. The secondary reformer is an autothermal reformer (ATR), which requires oxygen for partial oxidation reactions. In this configuration, oxygen has traditionally been supplied by introducing air, as shown in Figure 2 . The nitrogen that enters with the air remains in the process to be reacted with hydrogen in the ammonia synthesis loop. Following the reformers, high-temperature shift and low-temperature shift reactors convert carbon monoxide (CO) and steam to hydrogen and CO 2 . Subsequently, the CO 2 is removed using absorption and desorption in a solvent. The CO 2 must be removed from the gas stream prior to ammonia synthesis since any oxygen-containing molecules such as CO 2 , CO, and water (H 2 O) would poison the ammonia synthesis catalyst. Hot potassium carbonate (HPC) is commonly used for this pre-combustion CO 2 capture application. After removing most of the CO 2 from the gas stream, there are drying and methanation stages. Methanation converts any residual CO and CO 2 to methane (CH 4 ) through a reaction with hydrogen, which is present in the gas mixture.

Leaving the methanation reactor, the gas is a mixture of nitrogen and hydrogen, with small amounts of methane and argon. Methane and argon are removed using a cryogenic nitrogen wash, such as the technology used in the KBP Purifier ammonia process. This purge gas can be burned in the SMR to yield heat for the reforming reactions. The Burrup Fertilizers Ammonia Plant in Australia, now owned by Yara, was commissioned in April 2006. At that time, it was the largest implementation of the KBR Purifier process. The maximum ammonia production capacity is 2,600 tonnes per day (t/d). In 2019, EuroChem Group AG started up a new 2,890 t/d ammonia plant based on KBR’s Purifier ammonia technology. The facility is the largest ammonia plant in Europe. The CO 2 emissions from either the Burrup or EuroChem ammonia plant would be more than 2,000,000 tonnes per year (t/a). Since this CO 2 must be removed from the process to enable ammonia synthesis, there is no additional capital or operating cost associated with the CO capture aspect of CCS. With a small incremental investment in CO 2 drying and compression, CO 2 from ammonia facilities can be transported by pipeline to a suitable sequestration location. Nitrogen and oxygen production for ammonia synthesis An alternative pathway for ammonia synthesis is to react pure nitrogen and pure hydrogen

Burner ue gas

Air

CO

Purge gas

Natural gas feed

Haber-Bosch ammonia synthesis reactor

CO desor- ption

Steam

Super- heated steam

Feed compressor

Steam generation

Hydrogen

ATR

Purge gas

High temp. shift

Hydrogen- ation

SMR

Condenser

Catalyst bed

Phase separator

Steam generation

Raw syngas

Low temp. shift

Sulphur removal

Cryogenic heat exchanger

NH

Boiler feed water

Recycle compressor

Liquid ammonia

Fuel Air

Distillation column

Condensate

Feed preparation

Reforming

CO removal

Methanation and cryogenic nitrogen wash

Ammonia synthesis

Ammonia liquefaction and storage

Water gas shift reactors

Figure 2 Air-fed ammonia production process

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