Hi Seaweedman,
Just of the top of my mind methane is the simplest (bio)fuel, it has a low caloric value and is a bulk product. It might be that the costs of releasing, collecting, compressing and storing it do not add up to a profitable business, unless you do it on a really huge scale. But as an integrated concept on your site it might help you cut costs in heating your algae tanks (if they require any heating?). My best guess would be to remove from the algae all the valuables like the hydrocolloids (agar, carrageenan, alginates etc.), oils (good source for poly-unsaturated fatty acids) and using the remainder to extract the methane from.
For seaweeds some work was done and again the FAO has a a report on it. In chapter 9 and scroll about halfway down:
http://www.fao.org/DOCREP/006/Y4765E/y4765e0c.htm#TopOfPage
From the comments there it suggests that one has to anearobically digest the biomass in order to generate sufficient methane. The above link also gives some basic processes on how to remove and purify the hydrocolloids (but you probably know this already). The literature quoted sounds interesting as well. If you have trouble getting it, please let me know (I might be able to get it for you).
Best regards, Carbon-trader