The ash remain after gasification contains a number of compounds(mainly oxides I guess). The relative amount of these compounds decides the value of Bed Agglomeration Index(BAI) and Alkali Index(AI).
To get an idea of the composition, you must use a combination of at least two techniques. XRF can give you some elementary composition if you do not have low-atomic number elements. If you want to have higher accuracy and want to identify light elements as well, ICP-OES is the best option. Once you have the elementary composition, you can use XRD to identify the different crystals (and therefore the different compounds) contained in your sample. If you do XRD without knowing elementary composition (either from XRF , ICP-OES or from others like EDX) you may assign wrongly the peaks found in the XRD.