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In this study 4 different acid catalysts were prepared and mixed with commercial CZA catalysts and investigated in direct DME synthesis. Some of the used acid catalysts were not investigated in the literature therefore the work involves novelty. In a fixed-bed reactor, dimethyl ether (DME) was synthesized from the synthesis gas on two catalysts from, natural clinoptilolite and zeolite catalysts. The clinoptilolite (HK and DK) and two (HZSM5(117) and HZSM5(360)) catalysts mixed with commercial CuO/ZnO/Al 2 O 3 (CZN) catalysts. The catalysts were also characterized by analytical chemistry techniques such as XRD, BET, TGA, and FTIR. Four different catalysts (HK, DK, HZSM5(117) and HZSM5(360)) and CZA catalysts were mixed at a ratio of 3/1, respectively, and studies were carried out in a fixed-bed reactor. Four different catalyst composition activity tests were made at temperatures 250, 275, and 300 °C. At the same time, the pressure was 30 and 40 bar and four different times (30, 60, 90, and 120 min). The composition of the gases fed to the system for DME was adjusted to N 2 /CO 2 /CO/H 2 = 36/10/18/36 by volume. DME selectivity (S DME) and total carbon (X C) conversion were calculated for each condition. The experimental results showed that the highest DME selectivity of 96.50% was observed in the reaction of the DK + CZA catalyst mixture at 250 °C and 30 min at 40 bar. In addition, high DME selectivity was obtained in all reactions of DK + CZA and HK + CZA catalyst compositions at three different temperatures. The highest DME selectivity obtained is 89.69% for the reaction of the HK + CZA catalyst mixture at 300 °C and 60 min at 30 bar. Experimental results gave insights into Dimethyl ether synthesis from syngas on clinoptilolite zeolite and HZSM5-based hybrid catalysts in a fixed-bed reactor. • Dimethyl ether was synthesized from the synthesis gas on clinoptilolite and zeolite catalysts in a fixed-bed reactor. • Experimental results gave valuable insights on Dimethyl ether synthesis from syngas on clinoptilolite zeolite. • The clinoptilolite based catalysts and H-ZSM5(117) and H-ZSM5(360) catalysts mixed with commercial CuO/ZnO/Al2O3 catalysts. • The highest DME selectivity of 96.50% was obtained in the reaction of the DK + CZA catalyst mixture at 250 °C and 30 min. • The highest DME selectivity was 89.69% for the reaction of the HK + CZA catalyst mixture at 300 °C and 60 min and 30 bar. [ABSTRACT FROM AUTHOR]