The 5 km (3 mile) stretch of pipeline was transporting naphtha, primarily used as a feedstock for producing gasoline, when it began to leak around midday. Passersby had begun collecting the highly flammable liquid, when a sudden fire broke out at 2 pm (1400 GMT), spokeswoman Aba Lokko told journalists.
The fire sent a column of dense black smoke billowing hundreds of metres into the sky above Tema, around 20 km (12 miles) east of Accra.
Witnesses told Reuters they had seen the charred body of the victim of the accident. Lokko said the person was not an employee of the refinery.
The fire was brought under control in around three hours and output from the refinery would not be disrupted.
"Products supplies to the refinery will not be affected in any way, shape or form," Lokko said.
The fire also damaged part of Cocoa Processing Company's nearby factory forcing it to shut down. The facility has capacity to process 64,500 tonnes of cocoa beans annually.
"Our engineers are on the ground doing the initial assessment, but what we can say immediately is that the fire has damaged our packaging materials," CPC spokesman Ekow Rhule, told Reuters.
"The main power cable feeding the factory is also affected so we are not running the plant this evening," he added.
The refinery has been hobbled by repeated shutdowns over the last few years, but Ghanaian President John Mahama said in February that Tema was close to signing a joint venture agreement with PetroSaudi International.
The refinery's managing director was in London at the time of the accident as part of a delegation meeting with PetroSaudi to conclude the deal, Lokko said.
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