I'm trying to do the same with no luck yet, but I find out where the payment_redirect_key is created. You can found it in the function commerce_payment_redirect_pane_checkout_form in the commerce/modules/commerce_payment/includes/commerce_payment.checkout_pane.inc function commerce_payment_redirect_pane_checkout_form, line 360 of the current version (http://cgit.drupalcode.org/commerce/tree/modules/payment/includes/commerce_payment.checkout_pane.inc#n360)
Basically, is this:
$order->data['payment_redirect_key'] = drupal_hash_base64(time());
commerce_order_save($order);
EDIT
After a couple days working on this, I found the solution in just a few lines of code. I use this function as a page callback of a menu item (something like product/%sku). Here is the code:
<?php
function custom_module_create_order($sku) {
global $user;
$product = commerce_product_load_by_sku($sku);
$order = ($user->uid) ? commerce_order_new($user->uid, 'checkout_checkout') : commerce_cart_order_new();
// Save to get the Order ID.
commerce_order_save($order);
$line_item = commerce_product_line_item_new($product, 1, $order->order_id);
commerce_line_item_save($line_item);
$order_wrapper = entity_metadata_wrapper('commerce_order', $order);
$order_wrapper->commerce_line_items[] = $line_item;
// Select here the payment method. Usually something like:
// [module_name]|commerce_payment_[module_name]
$order->data['payment_method'] = 'commerce_sermepa|commerce_payment_commerce_sermepa';
commerce_order_save($order);
// Set status to order checkout to go to the payment platform redirect.
commerce_order_status_update($order, 'checkout_payment');
drupal_goto('checkout/' . $order->order_id);
}