Since, you don't enable centralized mail transport, the Exchange online will sent email to the Internet directly. For Exchange on-premises regardless of whether centralized routing is enabled, it always sent email to the Internet directly. So, your hybrid configuration doesn't effect the way of relay email in your organization.
If you want to relay email from Exchange on-premises Exchange, this article will be useful to you create a correct relay connector: How to Configure Exchange Server 2016 for SMTP Application Relay
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If you want to relay email from Exchange online, this article will be useful to you: How to set up a multifunction device or application to send email using Microsoft 365 or Office 365
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