ここを参考に。
http://qiita.com/ironsand/items/10e28d7589298090ec23
~/.zshrcに以下を追加
path_append () { path_remove $1; export PATH="$PATH:$1"; } path_prepend () { path_remove $1; export PATH="$1:$PATH"; } path_remove () { export PATH=`echo -n $PATH | awk -v RS=: -v ORS=: '$0 != "'$1'"' | sed 's/:$//'`; }
$ source ~/.zshrc $ path_remove PATH_TO_REMOVE