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@Br.louis - when you used the installed version of calibre, was it the 32bit or 64 bit edition? And how much RAM does your computer have.
Why do I ask? Well, the portable version of calibre is in fact the 32 bit version with a 'special' launcher. It's the 32bit version because its design target is a USB thumb drive which can be plugged into whatever Windows computers happens to be available (think internet cafés). There's no way of knowing if they will be capable of running 64 bit programs - in other words it's a lowest common denominator solution.
Now, if you installed the 64 bit edition, and your computer has say 6 Gig of RAM, that might account for the difference in behaviour. 32bit bit Windows programs can only address about 4 Gig of RAM. while 64 bit Windows programs can address almost 200 Gig of RAM.
So, maybe the solution is to use the 64bit edition of calibre and get more RAM.
It might be worth having a look at Sigil's TOC building capabilities, I'm not inferring it is better than calibre's, only that that it may not suffer the same limitations in this particular respect. Sigil is limited to ePub, so you'd need to convert the DOCX to ePub first.
BR
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