The study investigates the properties of industrial-scale supported copper-containing catalysts, H3-11 and MAK-K, in the dehydrogenation of cyclohexanol. These catalysts differ in the mechanism employed for the active component’s immobilization on a silica support: physically bound in the former case and chemically bound in the latter. Within set ranges of temperatures and space velocities (200–250°C, 0.5–2.0 h–1), data were obtained on the conversion rates and selectivity values provided by both catalysts, as well as on corresponding variations in by-product compositions. The trends for both catalysts were found to be similar. The kinetic data were processed using an equation previously suggested for a mixed copper-magnesium catalyst. This equation was confirmed to be able to describe kinetic experiments on the catalysts under study, regardless of the preparation method of a copper-containing catalyst and of the binding mechanism used for the supported active component. Macrokinetic properties were calculated for an industrial-scale reaction mixture and catalyst grain size.

The reported data relate to the influence of the nature of the aluminosilica support and of the temperature of its treatment with the ammoniaccarbonate solution containing ammoniac-carbonate complex of copper on the specific surface area, chemical and phase composition of the precursor of the active component and on the properties of copper-containing catalyst for dedhydrogenation of cyclohexanol. Elevation of the treatment temperature of amorphous silica (white carbon) with the ammoniac-carbonate solution results in an increase in the proportion of the chemically anchored precursor up to its complete bonding to the support to form the immobilized phase. A higher thermostability of the catalyst supported on white carbon with boehmite compared to the catalysts supported on pyrogenous silica is demonstrated.

Main characteristics of currently used industrial catalysts and an innovative catalyst MAK-K for dehydrogenation of cyclohexanol were compared. Main attention was paid to comparison of the activity and selectivity of MAK-K and the best catalyst H3-11 (BASF) at 220–270 °C and feed flow rate of 0.6–1.3 h–1. Similar behaviors were characteristic of both catalysts, the use of MAK-K being preferable at lower temperatures and higher feed flow rates. The MAK-K catalyst manufactured by LLC «NIAP-KATALIZATOR» was tested. The catalyst (1.4 m3) was loaded to a reactor for dehydrogenation of cyclohexanol at Shchekinoazot Co. and employed for more than 2000 h to demonstrate its high activity and selectivity. The catalyst was competitive against all the samples under study.

The influence exerted by the synthesis conditions and composition of a copper-containing nanostructured catalyst for cyclohexanol dehydrogenation on its textural characteristics, activity, and thermal stability was studied. The content of copper in the hydroxocarbonate form and the textural characteristics of the catalyst increase with increasing temperature of the precursor deposition onto the support. The presence of aluminum oxide in the system enhances the thermal stability of the catalyst. High activity, selectivity, and thermal stability of the catalyst obtained allow recommending it for commercial production as an alternative to the imported catalyst.

The effect of the hydrodynamic regime in the stirring of a copper carbonate–ammonia suspension containing an alumina–silica support on the chemical and phase composition of an active component (AC) precursor for a catalyst of cyclohexanol dehydrogenation to cyclohexanone is studied. By means of X-ray diffraction, differential thermal analysis, and adsorption, the precursor is found to precipitate in a developed turbulent regime, predominantly in the form of nanostructured hydroxocarbonate structures strongly bonded to the support. Some catalytic and textural properties of CAS-C (copper–alumina–silica for caprolactam) samples are studied with AC contents of 20 to 30 wt % (on a copper oxide basis). The laboratory technology is scaled up to industrial conditions. CAS-C samples and commercial H3-11 catalyst (BASF) are subjected to catalytic tests (in a flow-type reactor with a fixed catalyst bed 40 cm3 in volume at a temperature of 250°C and atmospheric pressure). The CAS-C catalyst is shown to be similar to the H3-11 catalyst in terms of selectivity, and to considerably surpass it in activity and thermal stability.

The influence of hydrodynamic mode of mixing a copper-ammonium-carbonate slurry containing aluminosilica support on the chemical and phase composition of the active component (AC) precursor of the catalyst for dehydrogenation of cyclohexanol in the production of caprolactam was studied. XPS, DTA and adsorption techniques were used to establish that, under conditions of the advanced turbulent mode, the precursor is mainly deposited in the form of nanostructured hydroxocarbonates anchored tightly to the support. The lab-scale technology was scaled-up to industrial level. Properties of the new copper catalyst were studied to reveal that it is not inferior in the selectivity to the best known industrial (commercial) catalysts, but superior to them in the activity and thermostability.