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Replication to an HTTP repository is actually done by copying to a UNC share, so the account you specify here needs to be an AD account with read/write access to the share, as opposed to an ePO account.
A couple of things to note with your proposed solution:
1) When configuring the DMZ server's distributed repo, make sure you confirgure it to only replicate updatable content, like DATs and engines. Whatever you do, do not replicate the agent package: otherwise you run the risk of the machines controlled by the primary server suddenly moving to the DMZ server.
2) You will need to export the DMZ server's repository public key, and import it into the primary server - otherwise it will not accept the DMZ server's content.