The blast took place in the city's Lunga Lunga industrial area, and police and troops cordoned off the area as firefighters battled fierce flames in the surrounding shanty town.
The pipeline runs through the densely populated Sinai slum area between Nairobi's city centre and the airport.
More than 80 casualties have been taken to hospitals, officials said.
Reports suggest Monday's blast may have been sparked by a cigarette butt being thrown into an open sewer that was filling with fuel.
The fuel had leaked from a tank in a depot belonging to the Kenya Pipeline Company, police spokesman Charles Owino told Reuters news agency.
Residents said the spill prompted many people to rush and collect leaking fuel.
"Then there was a loud bang, a big explosion, and smoke and fire burst up high," resident Joseph Mwego told Agence France-Presse.
Parts of bodies littered the remains of burning shacks for some 300m (1,000ft) around the site of the blast, locals said.
Bodies were also seen floating in a nearby river, into which burns victims had reportedly leapt after catching fire.
Tin-roofed huts were built directly adjacent to the pipeline in the area, residents say.
There have been other deaths involving people collecting leaking fuel.
More than 100 people died in Molo, western Kenya, in 2009 after a fire on an overturned tanker.
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