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Unique column combinations of a relational database table are sets of columns that contain only unique values. Discovering such combinations is a fundamental research problem and has many different data management and knowledge discovery applications. Existing discovery algorithms are either brute force or have a high memory load and can thus be applied only to small datasets or samples. In this paper, the wellknown GORDIAN algorithm and "Apriori-based" algorithms are compared and analyzed for further optimization. We greatly improve the Apriori algorithms through efficient candidate generation and statistics-based pruning methods. A hybrid solution HCAGORDIAN combines the advantages of GORDIAN and our new algorithm HCA, and it significantly outperforms all previous work in many situations.