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1, furfural method - from furfural decarbonylation to furan, and then hydrogenated. This is one of the first methods of industrial production of tetrahydrofuran. Furfural is mainly produced by hydrolysis of agricultural by-products such as corn cob. The law is seriously polluted and is not conducive to large-scale production and has been gradually phased out.
2, maleic anhydride catalytic hydrogenation process - maleic anhydride and hydrogen from the bottom into the reactor containing nickel catalyst, the ratio of tetrahydrofuran and γ-butyrolactone in the product can be controlled by adjusting the operating parameters. The reaction product and the raw material hydrogen are cooled to about 50 ° C to enter the bottom of the scrubbing column, and the unreacted hydrogen and gaseous state are separated from the liquid product. The unreacted hydrogen and gaseous products are washed and recycled to the reactor, and the liquid product is distilled to obtain a tetrahydrofuran product. . The process can arbitrarily adjust the ratio of γ-butyrolactone to tetrahydrofuran in the range of 0 to (5:01), the single pass conversion of maleic anhydride is 100%, the selectivity of tetrahydrofuran is 85%~95%, and the product content is 99.97. %. The process has the characteristics of good catalyst performance, simple process and low investment.
3, 1,4-butanediol dehydration cyclization method - the process is: adding 1087kg of 22% sulfuric acid aqueous solution to the reactor, adding 1,4-butane at 100 ° C at a rate of 110kg / h The alcohol, the temperature at the top of the column was maintained at 80 ° C, and an aqueous solution containing 80% of tetrahydrofuran was obtained from the top of the column at a rate of about 110 kg / h. After the addition of 50 t of 1,4-butanediol, about 70 kg of pyrophoric material was removed from the reactor. The pyrophoric acid is filtered, and the obtained aqueous sulfuric acid solution can be reused, and the yield of tetrahydrofuran in this process can reach 99% or more. Sulfuric acid is the earliest catalyst used in the industrial production of tetrahydrofuran, and it is also a catalyst which is widely used in production today. The process technology is mature, the process is relatively simple, the reaction temperature is low, and the yield of tetrahydrofuran is high, but sulfuric acid is easy to corrode equipment and pollute the environment.
4, Dichlorobutene method - using 1,4-dichlorobutene as raw material, hydrolysis to form butene diol, and then catalytic hydrogenation to obtain 1,4-dichlorobutene in hydration Hydrolysis in the sodium solution, formation of butenediol at 110 ° C, centrifugation to remove sodium chloride, concentration of the filtrate in an evaporative crystallizer, separation of the alkali metal carboxylate, and removal of high boilers in the distillation column. The purified butene diol is sent to the reactor, and the butene diol is hydrogenated to form butane diol at a temperature of 80 to 120 ° C and a certain pressure, and is distilled into a cyclone reactor at atmospheric pressure. And crude tetrahydrofuran is formed in an acidic medium at 120 to 140 ° C, dehydrated and deaerated, and finally distilled to obtain high purity tetrahydrofuran. The method is simple in operation, mild in condition, high in yield, small in amount of catalyst, and can be continuously used.
5, butadiene oxidation method - using butadiene as raw material, obtained by oxidation of furan, and then hydrogenated. This law has been industrialized abroad.
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