Elucidating the deactivation mechanism of beta zeolite catalyzed linear alkylbenzene production with oxygenated organic compound contaminated feedstocks.

Zeolite catalyzed alkylation of benzene with long-chain α-olefins is a promising method for the detergent industry. Considering the long-chain α-olefins from Fischer-Tropsch synthesis always contain some oxygenated organic compounds, the effect of which on the alkylation of benzene with 1-dodecene was comprehensively investigated over beta zeolite herein. -heptanol, -heptaldehyde and -heptanoic acid were selected as the model oxygenated organic compounds, and it was revealed that an obvious decrease of lifetime occurred when only trace amount of oxygenated organic compounds were added into the feedstocks. The deactivated catalyst was difficult to regenerate by extraction with hot benzene or coke-burning. A series of characterization tests complementary with DFT calculations revealed that the deactivation was mainly caused by the firm adsorption of oxygenated organic compounds on the acid sites. Further, comparison with the open-framework MWW zeolite revealed a similar effect of oxygenated organic compounds and deactivation mechanism for both beta and MWW, but beta is less sensitive to the oxygenated organic compounds. The main reason lies in the three-dimensional framework of beta, wherein the much higher adsorption energy of 1-dodecene makes it difficult to be replaced by oxygenated organic compounds. Additionally, beta could be regenerated more easily by extraction with hot benzene compared with MWW. But coke-burning caused a sharp decrease of its lifetime, which is mainly due to the decreased acid sites after calcination.