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Thank you for your inquiry.
To load properly license file should be accessible on the file system. In most cases we recommend deploying it to one disk folder with Aspose.Words.dll or in folder treated as current for the application. In particular, deploying a web service you can put it to the so named root application directory. Of course logon Windows account of the process must have enough permission to read the file from the underlying Windows folder.
Web service maps its application root to some disk folder. Mapping could be performed programmatically:
string realPath = Server.MapPath(Aspose.Words.dll'');
This path should be passed to LoadLicense. You can ensure that the file is present there first:
// do something
Please check this and if you still experience difficulties post here in any schematic form the directory tree of your site and show where you are putting the DLL and the license file.