Have you verified a methane problem by testing, and not just based on a bad smell. Methane is odourless but often accompanied by hydrogen sulphide (bad egg smell)
Treating the smelly part would be simpler if there was no major methane problem.
I assume below that you have detected methane.
The best solution is, as Rick noted, to vent the surrounding ground. Drill boreholes and fit a wind powered extractor on top of each borehole. (Think factory roof)
This could be expensive and aesthetically undesirable. Alternately use a caulking compound on the joints, google search for (tunnel caulking "asbestos free"

I can vouch for PC4 AF.
Methane is explosive at between 5.3% and 14%. Gas monitors normally display %LEL (5.3% methane is considered as 100% LEL)
Legislation in your country will probably apply if man entry takes place at levels over 5% LEL (0.25%)
Take any man entry into this pipe very seriously, "confined space" good practice including ventilation and gas monitoring, no hot works / sparks / smoking, electrical equipment selection etc are essential. Read relevant codes of practise e.g. BS6164, 5345 et al if youre in UK or possibly Bureau of Mines in your country.
If the gas level is over 5.3% any spark will kill every man in the pipe, take care.