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Before you can validate an ePub you actually need to create an ePub. A Word document is not an ePub.
I suspect that you're working on something to be published through Smashwords. The only way to check that your Word document is correctly formatted for Smashwords is to sumbit it at Smashwords, and see what they generate.
Reading and following their instructions to the letter make it more likely that you'll get a good result.
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