The error says it all:
Duplicate entry ''
So run the following query:
SELECT unique_id,COUNT(unique_id)
FROM yourtblname
GROUP BY unique_id
HAVING COUNT(unique_id) >1
This query will also show you the problem
SELECT *
FROM yourtblname
WHERE unique_id=''
This will show you where there are values that have duplicates. You are trying to create a unique index on a field with duplicates. You will need to resolve the duplicate data first then add the index.
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