No, they only pick up blocks that are in the world
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22 for skeletons, zombies and creepers however endermen take more.
Simply place it down and right click on it. There, you will be able to put stuff in it and take stuff out.
You take the whole stack, and right click the stack onto a free inventory, crafting, furnace or chest slot. This will remove one item from the stack, and can be repeated if more items are to be seperated.
In minecraft, it is necessary to build a crafting table. A crafting table lets you have a 3x3 crafting space to build in. To build it, you take bark, then put it in your personal crafting table in your inventory to get wooden planks, then use those wooden planks by putting then in your inventory crafting table, in a 2x2 format. Out comes your crafting table.
You take what you want and put near the section where the book bag is and it will show up and and click on it to put it inside