select unique is not valid syntax for what you are trying to do
you want to use either select distinct or select distinctrow
And actually, you don't even need distinct/distinctrow in what you are trying to do. You can eliminate duplicates by choosing the appropriate union statement parameters.
the below query by itself will only provide distinct values
select col from table1
union
select col from table2
if you did want duplicates you would have to do
select col from table1
union all
select col from table2