A first withdrawal may be slower, and will only be made once you have been verified. If 32Red are not able to do this electronically, you will have to submit documents. If in doubt, contact their CS this morning to find out whether they are going to process it today, or will want some information from you.
I believe the default pending period is 6 hours, but you can have this reduced to 1 hour, effectively having "autoflush" set on all withdrawals so that you do not have to keep pestering support. After this, withdrawals are normally processed and arrive the following day, however I have even experienced same day arrival in my Neteller account in the past for withdrawals made early in the day. 32Red process 7 days a week, although I think they don't process on Christmas day and new years day - but neither does anyone else.