Reactions Of Calcium Carbide And Calcium Alkoxide With Lower Alcohols To Formulate Higher Alcohols

With exhaustion of the petroleum and natural gas in the world, it is an effective way to make up the shortage of petrochemical materials from acetylene produced by calcium carbide originated from coal. The development of producing chemicals from coal and synthesizing calcium carbide by oxygen thermal process further promoted the downstream products exploitation of calcium carbide. Until now, the calcium carbide based technologies are, however, all via acetylene, which require pre-conversion of calcium carbide by reacting with water. The notable ones include the production of polyvinyl chloride, vinyl acetate and acetylene black. Nowadays, since calcium carbide and acetylene both have a C-C triple bond, scientists focus on the new methods of directly synthesizing such downstream products. In1960s, a patent about ethyl vinyl ether production from reaction of calcium carbide and alcohols were disclosed, but had not much notice. Recently, my group did further exploration and detailed illustrated the synthetic mechanism and found that Vinyl ethers chemicals were actually derived from acetylene reacting with alcohols, and acetylene was generated from the reaction between calcium carbide and alcohols. Besides, butanol was observed as well, it was initially considered deriving from the decomposition of calcium ethoxide, but not be further confirmed.Butanol, as a significant chemical raw materials, has been widely used as painting solvent, precursor of DBP and was considered as a potential biofuel. This work focus on the reactions between calcium carbide and calcium ethoxide with ethanol, we systematically studied the reaction behaviors under different reaction conditions and presented the synthetic process of butanol. Moreover, we exploringly studied the reaction between calcium carbide and calcium ethoxide with methanol. From this work, we can draw a conclusion as below:(1)Butanol can be produced in the reaction between calcium carbide and ethanol, which is not generated from the decomposition of intermediate product calcium ethoxide. According to our studies, the yield of butanol can reach26.7mmol after6h at360℃when the ethanol/calcium carbide(molar ratio) was19.3and the corresponding calcium carbide was23.6mmol.(2)Butanol can be produced in the reaction between calcium ethoxide and ethanol. The reaction temperature and reactant’s molar ratio were main influence factors on the amount of butanol. According to our studies, the yield of butanol can reach10.8mmol after9h at390℃ when the ethanol/calcium ethoxide(molar ratio) was33and the corresponding calcium ethoxide was6.58mmol.(3)Ethanol can be produced in the reaction between calcium carbide and calcium ehoxide with methanol at high temperature, the mechanism should be further studied.