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Q. Why does your guide say that decaffeinated coffee has to have hashgachah for Pesach? Why is the coffee more problematic if the caffeine was removed?
A. There are several methods of removing caffeine from coffee beans, and a common denominator between them is that the beans come in contact with a (hot) liquid which draws the caffeine out of the bean.
The liquid used for decaffeination may be water, a chemical solvent (i.e., ethyl acetate, methylene chloride, carbon dioxide), or a combination of the two. Sometimes water extracts the caffeine from the beans, and then the solvent is used to extract the caffeine from the water before the water is reused. In cases where the chemical solvent has direct contact with the beans, the beans are often soaked in hot water or steam to soften them before the solvent is applied.
The Pesach issues with these processes are that (a) ethyl acetate may be derived from chametz, and (b) the water used in the process is sometimes purified (hot) on a carbon bed, which is in turn purified with hot ethyl alcohol, which may be derived from chametz. Due to these concerns, decaffeinated coffee is only recommended on Pesach if it bears a reliable kosher certification, which guarantees that the decaffeination process has no traces of chametz or kitnios. [In addition to the issue of decaffeination, instant coffee and flavored coffee require hashgachah for Pesach.]