Esterification of free fatty acids using water-tolerable Amberlyst as a of heterogeneous acid catalysts, Amberlyst 15 and Amberlyst BD The grant supports Rohm and Haas’s development of a newly commercial polymeric catalyst technology, AMBERLYST™ BD20 specialty. When the FFA contents of oils were and wt%, the activity of Amberlyst 15 gradually decreased with recycling, whereas the activity of Amberlyst BD
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The method of claim 25further comprising the step of processing the second reaction mixture in one of a transesterification process and a hydrotreating process. The reaction should take place under sufficient pressure to maintain the alcohol in a liquid state at the desired reaction temperature.
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In ambrrlyst embodiment, a portion of alcohol, water, and homogenous catalyst 6 are removed from the second reaction mixture 5 contained in unit by decantation or centrifugation, leaving a principally dry reaction mixture 7.
Therefore, in one embodiment of this invention, the final FFA content of the reaction mixture leaving the process during steady state operation remains stable over time, that is, the final FFA content does not consecutively increase or decrease so as to create a trend.
The final FFA content of the oil phase began aberlyst In one embodiment the reaction is conducted using a 0.
In yet another embodiment, the amount of homogenous catalyst introduced to a reactor is between 0. The reaction can be summarized as follows: However, there are unresolved concerns about catalyst fouling, durability, stability, activity, and replacement schedule with continuous ambeflyst of commercial-grade higher FFA feedstocks.
The embodiments, variations, and figures described above provide an indication of the utility and versatility of the present invention. In one embodiment the pressure is maintained between 0 and psig.
The reaction is conducted using at least a stoichiometric amount of alcohol as determined on an FFA basis according to Equation 1. The method of claim 1wherein said reactor is a fixed bed reactor.
Esterification reactions can also be aided with excess alcohol and catalyst addition, although economic factors, small incremental improvements, and additional operational complexity usually limit their effectiveness. The flowrates provide a liquid hourly space velocity of 2.
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Potential causes of this steady deactivation include catalyst fouling and deactivation by proteins, phospholipids, metal ions, neutralization, chemical compounds i. For a variety of feedstocks and experimental conditions increasing hd20 FFA trends have been observed with Amberlyst ion exchange resin catalyst supporting the catalyst deactivation theory.
One method of the invention, with reference to FIG.
In one embodiment the regenerating acid flow in the opposite direction countercurrent of the service flow, noting the service flow may be upwards or downwards through the reactor. For instance it may be desirable to divide a fixed quantity of alcohol between amberylst and unitwith either equal or unequal portions of alcohol routed to each unit.
In any embodiment, dry reaction mixture 12 may continue to a transesterification, hydrogenation or other catalytic chemical conversion process, alcohol may be recovered from stream 11 and a portion of homogenous catalyst may be recovered from either stream 11 or The reaction can be summarized as follows:.
Methods, processes, apparatus, equipment and systems are disclosed for converting carboxylic acids into esters by esterification with alcohol and db20 dual catalyst. However, heterogeneous esterification activity is generally less than with homogeneous catalysts, and multiple stages or extreme operating conditions are typically required to achieve acceptable conversions.
US8957242B2 – Dual catalyst esterification – Google Patents
However, these equilibrium-limited reactions can be propelled further by increasing the concentration of the reactants or decreasing the concentration of the products. In one embodiment it may be beneficial to minimize the amount of homogenous catalyst in stream In another embodiment method is repeated in series with method In another embodiment, the residence time is between 5 and minutes.
In any embodiment, dry reaction mixture 7 may continue to a transesterification process, alcohol may be recovered from stream 6 and a portion of homogenous catalyst may be recovered from either stream 6 or 7.
The invention is illustrated in detail below with reference to the examples, but without restricting it to them. In one embodiment the second reaction mixture 5 is washed with water before entering a decanter This equates to a liquid hourly space velocity of 2.
The calculated molar ratio of methanol to free fatty acids was 8. Inedible corn oil with a free fatty acid content of A review of biodiesel production by integrated reactive separation technologies. The method of claim 1wherein said carboxylic acid content of the feedstock is between 0. The method of claim 1wherein the reactor is a continuous flow reactor.
In a vertical configuration, the reactants may flow upwards anberlyst downwards through the reactor In one embodiment the apparent residence time of reactants in the heterogeneous catalyst bed is between 2 and minutes. Free fatty acids in raw materials can also be esterified with alcohols using heterogeneous catalysis i.
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These feedstocks may or may not have been pretreated using means understood by one skilled in the art to remove impurities. Approximately g of feedstock was fed over 6. The FFA testing was completed as described in Example 2.