A method for continuously casting lithium-containing alloys by a direct chill process includes cooling the alloy to form a continuous ingot having a solid shell and further cooling the ingot by direct chill with an organic coolant. The organic coolant in one aspect includes a modified hydrocarbon fluid, e.g., ethylene glycol, having less than a predetermined moisture content. The method includes recirculating coolant while controlling moisture content. An ingot formed by the present invention provides small dendrite arm spacing in a relatively large size ingot.