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pspell_save_wordlist() saves the personal wordlist from the current session. The location of files to be saved specified with pspell_config_personal() and (optionally) pspell_config_repl().
<?php
$pspell_config = pspell_config_create("en");
pspell_config_personal($pspell_config, "/tmp/dicts/newdict");
$pspell_link = pspell_new_config($pspell_config);
pspell_add_to_personal($pspell_link, "Vlad");
pspell_save_wordlist($pspell_link);
?>