Here's a super basic example. I believe this will solve your problem, however, understand the logic.
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JavaScript is responsible for hiding the selected option and replicating it on the other selects. That way you do not have to be sending a post every time you select an option
$('.select').on('change', function() {
var option = $(this).val();
$('.select').each(function() {
$(this).find('option').show();
$(this).find('option[value=' + option + ']').hide();
});
});
<form action="#" method="POST">
<select class='select' name="select[1][]">
<option>Selecionar</option>
<option value='A'>A</option>
<option value='B'>B</option>
<option value='C'>C</option>
<option value='D'>D</option>
<option value='E'>E</option>
</select>
<select class='select' name="select[1][]">
<option>Selecionar</option>
<option value='A'>A</option>
<option value='B'>B</option>
<option value='C'>C</option>
<option value='D'>D</option>
<option value='E'>E</option>
</select>
<br>
<br>
<input type="submit">
</form>
In PHP = >
<?php
echo '<pre>';
print_r($_POST);
echo '</pre>';
exit;
/* Como o PHP vai capturar =>
[select] => Array
(
[1] => Array
(
[0] => A
[1] => B
)
)
*/
?>
NOTE: The result of this response is also based on the comments of your question.
I'm waiting for the feedBack.