Hydrogen and carbon dioxide coproduction

A process of recovering high purity gaseous hydrogen and liquid carbon dioxide comprising:

• (a) generating hydrogen from one or more hydrocarbons in a steam reformer;
• (b) treating the steam reformer effluent in a shift converter to convert carbon monoxide therein to carbon dioxide;
• (c) introducing the shift converter effluent into a hydrogen PSA unit thereby recovering gaseous hydrogen of at least 99.999 percent purity and an effluent stream comprising hydrogen, carbon dioxide, carbon monoxide and methane;
• (d) introducing the hydrogen PSA unit effluent stream at a pressure not exceeding 90 psia into a carbon dioxide PSA unit thereby producing a hydrogen-rich stream, a carbon dioxide-rich recycle stream and a carbon dioxide-rich product stream comprising at least 98 percent pure carbon dioxide;
• (e) recycling the hydrogen-rich stream to the feed to the steam reformer and concurrently optimizing the steam flow for the combined fresh and recycle feeds in order to increase generation of hydrogen in the reformer and thereby hydrogen production in the hydrogen PSA unit;
• (f) recycling the carbon dioxide-rich stream to the feed to the carbon dioxide PSA unit;
• (g) passing the carbon dioxide-rich product stream to a means of increasing pressure and thereafter to a means to liquify same under refrigeration and recovering therefrom a high purity liquid product and a waste stream;
• (h) recycling the waste stream from said liquifying means to the feed to the carbon dioxide PSA unit;
• and
• (i) withdrawing a portion of the high purity carbon dioxide from an intermediate point of said means of increasing pressure and recycling it to the carbon dioxide PSA unit;
• wherein said carbon dioxide pressure swing adsorption (PSA) unit contains at least two adsorbent beds and each adsorbent bed undergoes a cycle comprising pressurization with production of a hydrogen-rich stream, pressure equalization with another adsorbent bed, regeneration to produce a carbon dioxide-rich stream and pressure equalization with another bed, and said recycle stream under pressure in step (i) is utilized as a cocurrent purge to remove from the bed, components of the hydrogen PSA unit effluent that are less strongly adsorbed than carbon dioxide, thereby increasing the amount of carbon dioxide adsorbed in said bed, the purge being carried out prior to regeneration of said bed;
• and
• wherein, the production of high purity gaseous hydrogen is significantly improved at a low cost and there is substantially 100 percent conversion of the carbon content of the hydrocarbon feed to the steam reformer into carbon dioxide.