Graphical abstract for ethanol dehydration on the W-Ni-HZSM-5 catalys. Display omitted •Catalytic dehydration of bio-ethanol was analyzed over transition metals, loaded on HZSM-5, H-β zeolite, zirconium Aluminate.•Promising high conversion of bio-ethanol into potent fuel additive DEE with appreciable selectivity on 1 % W-5 %Ni-HZSM-5.•A 14.61% yield enhanced the desired diethyl ether synthesis due to 1% tungsten metal oxide loading on 5 %Ni-HZSM-5.•The catalyst was active and hydrothermally stable with efficient reusability and negligible coke deposition up to 5th cycles.•The study highlights the mechanistic comparison of the different acid catalysts with Lewis Bronsted acidic sites. Diethyl ether is an excellent additive in standard internal combustion engine fuel. The desired reaction product yield is more dependent on the type and strength of acidity of a catalyst for the higher selectivity of diethyl ether or ethylene. In the current work, the chemical process dehydration of alcohol was investigated successfully for forming diethyl ether and alkene over the synthesized tungsten-nickel-loaded catalysts. In present study synthesized different metal-loaded (Ni, W) on different supports (H-ZSM-5, β-Zeolite), and only weak acidic sites catalyst (with and without Ni loaded Zirconium aluminate) and compared all above synthesized catalyst for ethanol dehydration to diethyl ether at 7 h reaction time, 6 wt% catalyst dose, and 230 °C reaction temperature. Characterization using XRD, SEM-EDS, XPS, Raman-spectra, and BET-BJH revealed the appropriate synthesis of the catalyst and uniform Ni and W metal loading, resulting in increased catalytic performance. W-Ni metal oxide loading on H-ZSM-5 shows the most promising results than metal oxide loading on other support catalysts. A 14.61% yield enhanced the desired diethyl ether synthesis due to 1% tungsten metal oxide loading on 5 %Ni-HZSM-5. The XRD, FTIR, and TG-DTA analysis of reused 1 %W-5% Ni-HZSM-5 catalyst provides excellent reusability up to the fifth cycle of use, with a reusability efficiency of more than 96 % even up to the fifth reusability cycle. 1 %W-5 %Ni-HZSM-5 showed the best performance in a batch reactor for maximum diethyl ether synthesis from ethanol dehydration at a given reaction condition.