Manufacturing of bioethylene via dehydration of bioethanol is an alternative to the fossil-based ethylene production and decreases the environmental consequences for this chemical commodity. A few industrial plants that utilize 1st generation bioethanol for the bioethylene production already exist, although not functioning without subsidiaries. However, there is still no process producing ethylene from 2nd generation bioethanol. This study is divided into two parts. Different ethanol and ethylene production methods, the process specifications and current technologies are briefly discussed in the first part. In the second part, a techno-economic analysis of a bioethylene plant was performed using Aspen plus and Aspen Process Economic Analyzer, where different qualities of ethanol were considered. The results show that impurities in the ethanol feed have no significant effect on the quality of the produced polymer-grade bioethylene. The capacity of the ethylene storage tank significantly affects the capital costs of the process.

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Alkali-dissolution pretreatment of softwood spruce and hardwood birch to improve ethanol and biogas production was investigated. The pretreatments were carried out at different temperatures between −15 and 80• C with NaOH/thiourea (7/5.5 wt%), NaOH/urea (7/12 wt%), NaOH/urea/thiourea (7/8/6.5 wt%), and NaOH/PEG (7/1 wt%) aqueous solutions. The pretreated materials were then subjected to enzymatic hydrolysis for 72 h. The pretreatments by NaOH/thiourea at −15• C improved the hydrolysis yields of spruce from 11.7% to 57% of theoretical yield, and for birch from 23.

Combustion and synthesis of hydrocarbons may occur directly (CH → C + H and CO → C + O) or via a formyl (CHO) intermediate. Density functional theory (DFT) calculations were performed to calculate the activation and reaction energies of these reactions on Ni(111), Ni(110), and Ni(100) surfaces. The results show that the energies are sensitive to the surface structure. The dissociation barrier for methylidyne (CH → C + H: catalytic hydrocarbon combustion) is lower than that for its oxidation reaction (CH + O → CHO) on the Ni(110) and Ni(100) surfaces. However the oxidation barrier is lower than that for dissociation on the Ni(111) surface. The dissociation barrier for methylidyne dissociation decreases in the order Ni(111) > Ni(100) > Ni(110). The barrier of formyl dissociation to CO and H is almost the same on the Ni(111) and Ni(110) surfaces and is lower compared to the Ni(100) surface. The energy barrier for carbon monoxide dissociation (CO → C + O: catalytic hydrocarbon synthesis) is higher than that of for its hydrogenation reaction (CO + H → CHO) on all three surfaces. This means that the hydrogenation to CHO is favored on these nickel surfaces. The energy barrier for both reactions decreases in the order Ni(111) > Ni(100) > Ni(110). The barrier for formyl dissociation to CH + O decreases in the order Ni(100) > Ni(111) > Ni(110). Based on these DFT calculations, the Ni(110) surface shows a better catalytic activity for hydrocarbon combustion compared to the other surfaces, and Ni is a better catalyst for the combustion reaction than for hydrocarbon synthesis, where the reaction rate constants are small. The reactions studied here support the BEP principles with R(2) values equal to 0.85 for C-H bond breaking/forming and 0.72 for C-O bond breaking /forming reactions.

Catalytic combustion of hydrocarbons is an important technology to produce energy. Compared to conventional flame combustion, the catalyst enables this process to operate at lower temperatures; hence, reducing the energy required for efficient combustion. The reaction and activation energies of direct combustion of hydrocarbons (CH → C + H) on a series of metal surfaces were investigated using density functional theory (DFT). The data obtained for the Ag, Au, Al, Cu, Rh, Pt, and Pd surfaces were used to investigate the validity of the Brønsted-Evans-Polanyi (BEP) and transition state scaling (TSS) relations for this reaction on these surfaces. These relations were found to be valid (R2 = 0.94 for the BEP correlation and R2 = 1.0 for the TSS correlation) and were therefore used to estimate the energetics of the combustion reaction on Ni, Co, and Fe surfaces. It was found that the estimated transition state and activation energies (ETS = −69.70 eV and Ea = 1.20 eV for Ni, ETS = −87.93 eV and Ea = 1.08 eV for Co and ETS = −92.45 eV and Ea = 0.83 eV for Fe) are in agreement with those obtained by DFT calculations (ETS = −69.98 eV and Ea = 1.23 eV for Ni, ETS = −87.88 eV and Ea = 1.08 eV for Co and ETS = −92.57 eV and Ea = 0.79 eV for Fe). Therefore, these relations can be used to predict energetics of this reaction on these surfaces without doing the time consuming transition state calculations. Also, the calculations show that the activation barrier for CH dissociation decreases in the order Ag ˃ Au ˃ Al ˃ Cu ˃ Pt ˃ Pd ˃ Ni > Co > Rh > Fe.Electronic supplementary materialThe online version of this article (10.1007/s00894-018-3585-z) contains supplementary material, which is available to authorized users.

The effect of carbon monoxide (CO) co-adsorption on the dissociation of water on the Ni(111) surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O–H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O–H bond in the transition state structure has a larger imaginary frequency in the presence of CO. In addition, the distances between the Ni surface and H2O reactant and OH and H products decrease in the presence of the CO. The changes in structures and vibrational frequencies lead to a reaction energy that is 0.17 eV less exothermic in the presence of the CO, and an activation barrier that is 0.12 eV larger in the presence of the CO. At 463 K the water dissociation rate constant is an order of magnitude smaller in the presence of the CO. This reveals that far fewer water molecules will dissociate in the presence of CO under reaction conditions that are typical for the water-gas-shift reaction.

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