The correct answer is Option B.
MUSTN'T is the negation of MUST.
MUST expresses compulsion.
In the given sentence, it is compulsory to not block the door because it is a fire exit.
Thus MUSTN'T is the correct answer.
The remaining options are incorrect because:
SHOULDN'T is the negation of SHOULD. It expresses obligation.
CAN'T is the negation of CAN. It expresses ability.
COULDN'T is the past tense of CAN'T.