Process For The Production Of Hydrogen And Carbon Dioxide

Abstract

This present invention provides a method to more efficiently recover hydrogen and carbon dioxide, preferably at least 50%, even more preferably at least 75%, and most preferably at least 90% of the carbon dioxide. The present invention further provides the design for capture of at least 80%, carbon dioxide from syngas that allows for the simultaneous production of medium to high amounts of hydrogen in the syngas as a part of the production of hydrogen in a hydrogen generation plant. By using the process of the present invention, especially in terms of a hydrogen generation plant, it is possible to increase recovery of hydrogen and capture of the carbon dioxide in the syngas stream by balancing the recycle of the hydrogen rich permeate from the hydrogen membrane separation units to the process unit and/or the water gas shift as capacity allows when a carbon dioxide separation unit, a carbon dioxide membrane separation unit and two hydrogen membrane separation units are utilized.

1 . A process for producing hydrogen and capturing carbon dioxide from a hydrocarbon containing feed stream ( 20 ) in a hydrogen generation plant, the process comprising the steps of:
 a) treating a hydrocarbon containing feed stream ( 20 ) in a feed gas producing unit ( 34 ) to obtain a feed gas ( 19 );   b) subjecting the feed gas ( 19 ) to hydrogen purification in a process unit ( 0 ) to obtain a hydrogen product stream ( 27 ) and a hydrogen depleted process stream ( 1 );   c) withdrawing the hydrogen product stream ( 27 ) and using a portion of this hydrogen product stream ( 27 ) as a fuel for the feed gas producing unit ( 34 ) or as fuel for steam generation;   d) optionally compressing at least a portion of the process stream ( 1 ) in a first compressor ( 2 );   e) adjusting the temperature of the process stream ( 1 ) in a heat exchanger ( 3 ) to a temperature from 20° C. to 150° C.;   f) passing the temperature adjusted process stream ( 1 ) through a first hydrogen selective membrane separation unit ( 4 ) to form a first hydrogen rich permeate stream ( 5 ) with the remaining components in the process stream ( 1 ) forming a first hydrogen lean residue stream ( 6 );   g) optionally compressing the first hydrogen rich permeate stream ( 5 ) in a second compressor ( 17 ) and then recycling the first hydrogen rich permeate stream ( 5 ) for use as a supplemental feed stream in the feed gas producing unit ( 34 ) or the process unit ( 0 ) or both the feed gas producing unit ( 34 ) and the process unit ( 0 );   h) cooling the first hydrocarbon lean residue stream ( 6 ) in a heat exchanger ( 7 ) to a temperature equal to or less than −10° C.;   i) separating and purifying the cooled first hydrocarbon lean residue stream ( 6 ) in a carbon dioxide separation unit ( 8 ) to produce a carbon dioxide rich liquid stream ( 9 ) and a carbon dioxide lean non-condensable stream ( 10 );   j) withdrawing the carbon dioxide rich liquid stream ( 9 ) as carbon dioxide product for further use;   k) withdrawing the carbon dioxide lean non-condensable stream ( 10 ) from the carbon dioxide separation unit ( 8 ) and passing the carbon dioxide lean non-condensable stream ( 10 ) through a second hydrogen selective membrane separation unit ( 11 ) to form a second hydrogen rich permeate stream ( 12 ) with the remaining components in the carbon dioxide lean non-condensable stream ( 10 ) forming a second hydrogen lean residue stream ( 13 );   l) passing the hydrogen lean residue stream ( 13 ) through a carbon dioxide selective membrane separation unit ( 14 ) to form a carbon dioxide enriched permeate stream ( 15 ) with the remaining components in the hydrogen lean residue stream ( 13 ) forming a carbon dioxide depleted residue stream ( 16 ); and   m) optionally compressing the second hydrogen rich permeate stream ( 12 ) in a third compressor ( 28 ) and recycling the second hydrogen rich permeate stream ( 12 ) for use as a supplemental feed stream in the feed gas producing unit ( 34 ) or the process unit ( 0 ) or both the feed gas producing unit ( 34 ) and the process unit ( 0 ), recycling the carbon dioxide enriched permeate stream ( 15 ) to the process stream ( 1 ) prior to the compressor ( 2 ) or within the compressor ( 2 ) between stages of compression or optionally compressing the carbon dioxide enriched permeate stream ( 15 ) and recycling the carbon dioxide enriched permeate stream ( 15 ) to be used in the carbon dioxide separation unit ( 8 ) and recycling the carbon dioxide depleted residue stream ( 16 ) to be used as a fuel for the feed gas producing unit ( 34 ).   
     
     
         2 . The process of  claim 1 , wherein the overall capture rate of carbon dioxide from the hydrogen production process is equal to or greater than 80%. 
     
     
         3 . The process of  claim 1 , wherein the process unit ( 0 ) is a pressure swing adsorption unit and the process stream ( 1 ) is a tail gas from the pressure swing adsorption unit. 
     
     
         4 . The process of  claim 3 , wherein the first hydrogen rich permeate stream ( 5 ) is split into a primary fraction of the first hydrogen rich permeate stream ( 5 . 1 ) to be used as a supplemental feed stream to be added to the hydrogen containing feed stream ( 20 ) prior to being introduced into the feed gas producing unit ( 34 ) and a secondary fraction of the first hydrogen rich permeate stream ( 5 . 2 ) to be used as a supplemental feed stream to be added to the feed gas ( 19 ) prior to being introduced into the process unit ( 0 ) with the proportion of each fraction depending upon the percentage of production in the feed gas producing unit ( 34 ). 
     
     
         5 . The process of  claim 4 , wherein the primary fraction of the first hydrogen rich permeate stream ( 5 . 1 ) is optionally heated prior to being added to stream ( 20 ). 
     
     
         6 . The process of  claim 1 , wherein one or both of the following occur: the first hydrogen rich permeate stream ( 5 ) is subjected to a shift reaction in an optional second water gas shift reactor ( 38 ) prior to being recycled to the water gas shift reactor ( 25 ), the process unit ( 0 ) or in both the water gas shift reactor ( 25 ) and the second hydrogen rich permeate stream ( 12 ) is subjected to a shift reaction in an optional third water gas shift reactor ( 39 ) prior to being recycled to the water gas shift reactor ( 25 ), the process unit ( 0 ) or both the water gas shift unit ( 25 ) and the process unit ( 0 ). 
     
     
         7 . The process of  claim 6 , wherein each water gas shift reactor ( 38 ,  39 ) is a low temperature water gas shift reactor. 
     
     
         8 . The process of  claim 1 , wherein the process stream ( 1 ) and/or the carbon dioxide lean non-condensable stream ( 10 ) are subjected to a shift reaction in an optional fourth water gas shift reactor ( 40 ) prior to being passed thorough the first hydrogen membrane separation unit ( 4 ) or the second hydrogen membrane separation and carbon dioxide membrane separation units ( 11 ,  14 ). 
     
     
         9 . The process of  claim 8 , wherein the each water gas shift reactor is a low temperature water gas shift reactor.