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The crash, at a section of the Hukun (Shanghai to Kunming) highway in Shaoyang in Hunan province, happened in the early hours of Saturday when the van drove into the back of the passenger coach, triggering a fire and explosion, the official Xinhua news agency said.
Six people were injured, including four with severe burns. Five vehicles were destroyed, Xinhua said.
Last week, 11 people were killed, including eight children, when a school bus crashed into a reservoir in Hunan.
A series of accidents in recent years involving vehicles carrying school children have made such incidents a sensitive issue, particularly in China's rural areas where roads are often poorly maintained.