Hydrogen production via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system

Hydrogen production was prepared via catalytic steam reforming of fast pyrolysis bio-oil in a two-stage fixed bed reactor system. Low-cost catalyst dolomite was chosen for the primary steam reforming of bio-oil in consideration of the unavoidable deactivation caused by direct contact of metal catalyst and bio-oil itself. Nickel-based catalyst Ni/MgO was used in the second stage to increase the purity and the yield of desirable gas product further. Influential parameters such as temperature, steam to carbon ratio (S/C, S/CH₄), and material space velocity (W_BHSV, GHSV) both for the first and the second reaction stages on gas product yield, carbon selectivity of gas product, CH₄ conversion as well as purity of desirable gas product were investigated. High temperature (> 850 °C) and high S/C (> 12) are necessary for efficient conversion of bio-oil to desirable gas product in the first steam reforming stage. Low W_BHSV favors the increase of any gas product yield at any selected temperature and the overall conversion of bio-oil to gas product increases accordingly. Nickel-based catalyst Ni/MgO is effective in purification stage and 100% conversion of CH₄ can be obtained under the conditions of S/CH₄ no less than 2 and temperature no less than 800 °C. Low GHSV favors the CH₄ conversion and the maximum CH₄ conversion 100%, desirable gas product purity 100%, and potential hydrogen yield 81.1% can be obtained at 800 °C provided that GHSV is no more than 3600 h^− 1. Carbon deposition behaviors in one-stage reactor prove that the steam reforming of crude bio-oil in a two-stage fixed bed reaction system is necessary and significant.     

Hydrogen sulfide sensing properties of multi walled carbon nanotubes

This paper investigates the effect of functional groups on the hydrogen sulfide sensing properties of multi-walled carbon nanotubes using carboxyl and amide groups and Mo and Pt nanoparticles as decorated precursors in gaseous state at working temperature. Carbon nanotubes were synthesized by the CVD process and decorated with the nano particles; provide higher sensitivity for H₂S gas detection. The MWCNTs were characterized by scanning electron microscopy combined with energy dispersive X-ray (SEM/EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), ATR-IR absorption and Fourier transforms infrared (FT-IR) analyses. The MWCNTs were deposited as a thin film layer between prefabricated gold electrodes on alumina surfaces. The sensitivity of carbon nanotubes was measured for different H₂S gas concentrations and at working temperature. The results showed that the measured electrical conductance of the modified carbon nanotubes with functional groups is modulated by charge transfer with P-type semiconducting characteristics and metal decorated carbon nanotubes exhibit better performances compared to functional groups of carboxyl and amide for H₂S gas monitoring at room temperature.     

Hydrogen Sulfide-Resistant Bifunctional Catalysts for the Steam Reforming of Methane: Activity and Structural Evolution

Results are presented from studying an iron–nickel catalyst for the steam reforming of methane, synthesized by epitaxial coating on the surface of spherical pellets of commercial γ-Al₂O₃. It is shown the catalyst is resistant to the presence of hydrogen sulfide in a steam–gas mixture. The degree of conversion of methane during reforming is close to equilibrium at a pressure of 2.0 MPa, a temperature of 800°C, a ratio of Н₂О: СН4 = 2: 1, a feedstock hourly space velocity (FHSV) of 6000 h^?1, and a H₂S concentration of 30 ppm. The structural evolution and phase state of the active components of the system are studied via X-ray diffraction analysis, transmission electron microscopy (TEM), and Mössbauer spectroscopy. The formation of paramagnetic iron oxide clusters tightly bound to the structure of the support, and of FeNi₃ iron–nickel alloy particles on the surface of the catalyst, is responsible for the polyfunctional properties of the catalyst, which displays high activity in both the steam reforming of methane and the oxidative decomposition of hydrogen sulfide to elemental sulfur.     

Suppression of carbon formation in steam reforming of methane by addition of Co into Ni/ZrO2 catalysts

We investigated the steam reforming of methane (SRM) over various NiCo bimetallic catalysts supported on ZrO₂ to determine whether the addition of Co on the Ni catalyst suppressed carbon formation. The effect of metal loading on SRM reaction was evaluated in a downflow tubular fixed-bed reactor under various steam-to-carbon (S/C) ratios and temperatures. For monitoring changes in the catalysts before and after the SRM reactions, several techniques (BET, XRD, TEM, and CHN analysis) were used. The effects of reaction temperature, gas hourly space velocity (GHSV), and molar S/C ratios were studied in detail over the various catalyst combinations. It was found that an Ni- to-Co ratio of 50: 50 supported on ZrO₂ provided the best catalytic activity, along with an absence of coking, when operated at a temperature of 1,073 K, a GHSV of 24 L g⁻¹ h⁻¹, and an S/C ratio of 3: 1.     

Vanadium Oxide Based Nanostructured Materials: Novel Oxidative Dehydrogenation Catalysts

Novel vanadium oxide based catalyst derived from the open-framework solid, [Co₃V₁₈O₄₂(H₂O)₁₂(XO₄)]·24 H₂O (X = V, S) (1) catalyses oxidative dehydrogenation of propane to propylene. Catalyst activity was evaluated in the temperature range 250–400 °C with varying gas hourly space velocity (GHSV). At 350 °C and GHSV of 9786 h^?1 and at 1.3% propane conversion the selectivity to propylene was 36.8%. The major products obtained were propylene and CO _x (CO₂ and CO). The ratio of the propylene to CO _x depended directly on the catalytic sites present. Thus, as the amount of the catalyst was decreased, the conversion decreased with an increase in the propylene selectivity and a decrease in the selectivity to carbon oxides—CO _x . The catalyst has been characterized by temperature programmed reduction and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS).     

Oxidation of low concentrations of hydrogen sulfide over activated carbon

The oxidation of low concentrations of hydrogen sulfide with air over activated carbon was studied over the temperature range 24-200°C using both fixed and fluid bed reactors. The predominant reaction, H₂S + ½ O_a → H₂O + S, was found to have an order of 0.5 with respect of H₂S concentration. Activity of the catalyst decreased as the amount of sulfur deposited on it increased. Indirect evidence suggests that adsorption of water by the carbon also decreases its activity as a catalyst at lower temperatures. Values of the activation energy and the frequency factor were determined for various sulfur loadings using the fixed bed reaction system. Regeneration of the carbon loaded with sulfur was studied at temperatures between 150 and 500°C using steam as a carrier gas. Bright yellow sulfur was recovered. The regenerated carbon was shown to have its original activity.     

Fuel Gas Upgrading Over La1−xCexCoO3 Mixed Oxide with Toluene as Model Compound

Perovskite-type mixed oxides La_1?xCe_xCoO₃ (x = 0, 0.2, 0.4) were synthesized by sol–gel method via polyvinyl alcohol (PVA) as gelating agent. LaCoO₃ and CeO₂ phases were presented while intermediate phase, La(OH)₃, disappeared during LaCoO₃ transformation. Introduction of Ce decreased crystal size of catalyst from 22.18 to 13.38 nm. Particle size and specific surface area were in the range of 9.58–13.72 μm and 6.03–9.23 m²/g, respectively. The addition of Ce increased the reduction temperature which indicated the strong interaction between Co and perovskite structure. Catalytic activity was investigated by steam reforming of toluene at 500–800 °C. Conversions of carbon and hydrogen to CO, H₂, and CH₄ at steam per carbon ratio (S/C) of 2:1 were clearly higher than 4:1. Increasing S/C ratio to 4:1 inhibited syngas production efficiency by combustion and water–gas shift reaction. The presence of Ce in the catalyst did not improve activity of catalyst significantly. However the metal enhanced stability by promoting the formation of filamentous carbon on the surface such that the active sites are still accessible to the active gas during the experiment. After reforming, catalysts were transformed to La(OH)₃, Co⁰, and Ce₄O₇ phases and no significant deterioration in catalytic performance was detected after 6 h. In this study steam reforming of toluene over La_0.6Ce_0.4CoO₃ at 800 °C with S/C 2:1 yielded highest carbon conversion as CO and hydrogen conversion as H₂ of 64.42 and 63.23 %. The LHV and H₂/CO of produced gas at this optimum condition are 4.22 MJ/N m² and 2.91, respectively.     

Upgrading of Simulated Syngas by Using a Nanoporous Silica Membrane Reactor

The permeance properties of a nanoporous silica membrane were first evaluated in a laboratory‐scale porous silica membrane reactor (MR). The results indicated that CO, CO₂, and N₂ inhibited H₂ permeation. Increased H₂ permeability and selectivity were obtained when gas was transferred from the lumen side to the shell side. This was therefore selected as a suitable permeation direction. On this basis, upgrading of simulated syngas was experimentally investigated as a function of temperature (150 – 300 °C), feed pressure (up to 0.4 MPa), and gas hourly space velocity (GHSV), by using a nanoporous silica MR in the presence of a Cu/ZnO/Al₂O₃ catalyst. The CO conversion obtained with the MR was significantly higher than that with a packed‐bed reactor (PBR) and broke the thermodynamic equilibrium of a PBR at 275 – 300 °C and a GHSV of 2665 h^–1. The use of a low GHSV and high feed pressure improved the CO conversion and led to the recovery of more H₂.     

Kinetics and reaction mechanism of catalytic oxidation of low concentrations of hydrogen sulfide in natural gas over activated carbon

The kinetics of the hydrogen sulfide oxidation process, producing mostly sulfur and water, was studied using 0.25 to 1.0 g Hydrodarco activated carbon catalyst and varying the O₂/H₂S ratio (molar basis) in the feed gas between 0.5 to 0.6 in the temperature, and pressure ranges from 125 to 200°C and 225 to 780 kPa. SO₂ was obtained as an undesirable by-product during H₂S oxidation reaction or as a product during regeneration of the catalyst. The feed gas contained 0.9 — 1.3 mol% H₂S with approximately 80 mol% CH_4. In this paper, the factors affecting the H₂S conversion and SO₂ formation are presented. The rate expressions for (a) H₂S conversion and (b) SO₂ formation were developed from the Langmuir-Hinshelwood surface control reaction model. The experimental data were well correlated by the rate equations. Also, the rate parameters were evaluated and correlated with temperature. The activation energies for H₂S oxidation and SO₂ production reactions were calculated to be 34.2 and 62.5 kJ/mol, respectively. Partial pressures of oxygen and H₂S were found to influence H₂S conversion whereas, the presence of water in the feed gas up to 10.5 mol% did not affect H₂S conversion significantly. Heats of adsorption for various species on the active sites were calculated. SO₂ production was, as expected, enhanced at higher temperature, and its rate was much smaller than the oxidation rate of H₂S under the reaction conditions used.     

Kinetic Study of the Steam Reforming of Isobutane Using a Pt–CeO2–Gd2O3 Catalyst

Steam reforming of isobutane on a 0.5% Pt–Ce_0.8Gd_0.2O_1.9 catalyst was carried out from 300 to 700 °C under integral conditions with a gas hourly space velocity (GHSV) of 12,000 h⁻¹. The major products were H₂, CO₂, CO and CH₄. The other products produced were ethane, ethylene, propane and propylene with a total molar composition of less than 1.5%. A complete conversion of isobutane was achieved at 700 °C, Kinetic data was obtained by changing the partial pressure of the reactants and the temperature under differential conditions with a GHSV of 55,400 h⁻¹. This was done after observing stable isobutane steam reforming for 160 h and under conditions where the mass transfer limitations were insignificant. An empirical Langmuir–Hinshelwood type model that best fit the kinetic data available was developed.     

Biomass to hydrogen via catalytic steam reforming of bio-oil over Ni-supported alumina catalysts

Production of hydrogen (H₂) from catalytic steam reforming of bio-oil was investigated in a fixed bed tubular flow reactor over nickel/alumina (Ni/Al₂O₃) supported catalysts at different conditions. The features of the steam reforming of bio-oil, including the effects of metal content, reaction temperature, W_bHSV (defined as the mass flow rate of bio-oil per mass of catalyst) and S/C ratio (the molar ratio of steam to carbon fed) on the hydrogen yield were investigated. Carbon conversion (moles of carbon in the outlet gases to moles of the carbon feed) was also studied, and the outlet gas distributions were obtained. It was revealed that the Al₂O₃ with 14.1% Ni content gave the highest yield of hydrogen (73%) among the catalysts tested, and the best carbon conversion was 79% under the steam reforming conditions of S/C = 5, W_bHSV = 13 1/h and temperature = 950 °C. The H₂ yield increased with increasing temperature and decreasing W_bHSV; whereas the effect of the S/C ratio was less pronounced. In the S/C ratio range of 1 to 2, the hydrogen yield was slightly increased, but when the S/C ratio was increased further, it did not have an effect on the H₂ production yield.     

The effects of cobalt and cerium promoters on hydrogen production performance of alumina-supported nickel catalysts in propane steam reforming

BACKGROUND: The effects of Co and Ce promoters on the performance of Ni (10 wt%)–Co (0.0, 2.75, 5.5 wt%)/Ce (0.0, 5.0, 10.0 wt%)–Al₂O₃ catalysts have been studied for steam reforming of C₃H₈ (SRP). In this work, Ni (NO₃)₂ and Co (NO₃)₂ are co-impregnated on the co-precipitated Al₂O₃–CeO₂ supports. X-ray diffraction, N₂ adsorption–desorption, H₂-temperature-programmed reduction, high-resolution transmission electron microscopy, scanning electron microscopy and thermogravimetric/differential thermal analysis were accomplished to explain the SRP activity of the catalysts. The performance of the resulting catalysts was evaluated under the gas hourly space velocity (GHSV) = 45 000 mL h^-1 g_cat⁻¹, T = 600 °C, steam/C₃H₈ ratio (S/C) = 3 and P = 1 atm. RESULTS: The experimental findings revealed that Ce and Co promoters markedly improved the catalyst activity, stability and H₂ yield of Ni/Al₂O₃ catalyst. The sample with 2.75 wt% Co and 10.0 wt% Ce showed highest C₃H₈ conversion, while maximum yield of H₂ was obtained for catalyst containing 5.5 wt% Co and 5.0 wt% Ce. CONCLUSION: Higher loadings of Co decreased C₃H₈ conversion and catalyst stability due to more coke formation on the catalyst surface, whereas Ce significantly improved catalyst resistance to coke deposition due to the enhanced Ni metal particles distribution over the support. © 2020 Society of Chemical Industry     

Production of H2 and medium heating value gas via steam gasification of lignins in fixed‐bed reactors

In this work, steam gasification of Alcell and Kraft lignins were carried out in a fixed‐bed reactor in order to produce H₂ and medium heating value gas. The conversion of lignins increased from a low of 64 wt% for Alceil lignin to a high of 88 wt% for Kraft lignin with increasing steam flow rate and temperature. Maximum H₂ production of 60.7 mol% was obtained at 800°C and at a steam flow rate of 15 g/h/g of Kraft lignin, whereas maximum heating value of 18000 kl/m³ of the product gas was obtained at 650°C and at 5 g/h/g of Alcell lignin. Also, the performance of a Ni‐based steam reforming catalyst for the production of H₂ was studied for both types of lignin in a dual fixed‐bed reaction system. A maximum H₂ production of 63 mol% was obtained at a catalyst bed temperature of 750°C and at a catalyst loading of 0.3 g for Alcell lignin. The sulfur present in Kraft lignin had detrimental effect on the catalyst performance.     

Oxidation of low concentrations of hydrogen sulphide: Process optimization and kinetic studies

Low concentrations (e.g. < 3) of H₂ S in natural gas can be selectively oxidized over an “granular Hydrodarco” activated carbon catalyst to elemental sulphur, water and a small fraction of by-product sulphur dioxide, SO₂. To optimize the H₂ S catalytic oxidation process, the process was conducted in the temperature range 125—200 °C, at pressures 230—3200 kPa, with the O/H₂ S ratio being varied from 1.05 to 1.20 and using different types of sour and acid gases as feed. The optimum temperature was determined to be approximately 175 °C for high H₂ S conversion and low SO₂ production with an O/H₂ S ratio 1.05 times the stoichiometric ratio. The life of the activated carbon catalyst has been extended by removing heavy hydrocarbons from the feed gas. The process has been performed at elevated pressures to increase H₂ S conversion, to maintain it for a longer period and to minimize SO₂ production. The process is not impeded by water vapour up to 10 mol% in the feed gas containing low concentrations of CO₂ (< 1.0). A decrease in H₂ S conversion and an increase in SO₂ production were obtained with an increase in water vapour in the feed gas containing a high percentage of CO₂. The process works well with “sour natural gas” containing approximately 1% H₂ S and with “acid gas” containing both H₂ S and CO₂. It gives somewhat higher H₂ S conversion and low SO₂ production with feed gas containing low concentrations of CO₂. A kinetics study to determine the rate-controlling step for the H₂ S catalytic oxidation reaction over “granular Hydrodarco” activated carbon has been conducted. It was concluded that either adsorption of O₂ or H₂ S from the bulk phase onto the catalyst surface is the rate-controlling step of the H₂ S catalytic oxidation reaction.     

Steam gasification of coal with salt mixture of potassium and nickel in a fluidized bed reactor

Australian coal loaded with a mixed catalyst of K₂SO₄+Ni(NO₃)₂ has been gasified with steam in a fluidized bed reactor of 0.1 m inside diameter at atmospheric pressure. The effects of gas velocity (2-5 U_g/U_mf), reaction temperature (750-900 °C), air/coal ratio (1.6-3.2), and steam/coal ratio (0.63-1.26) on gas compositions, gas yield and gas calorific value of the product gas and carbon conversion have been determined. The product gas quality and carbon conversion can be greatly improved by applying the catalyst; they can also be enhanced by increasing gas velocity and temperature. Up to 31% of the catalytic increment in gas calorific value could be obtained at higher temperatures. In the experimental runs with variation of steam/coal ratio, the catalytic increments were 16-38% in gas calorific value, 14-57% in carbon conversion, 5-46% in gas yield, and 7-44% in cold gas efficiency. With increasing fluidization gas velocity and reaction temperature, the unburned carbon fraction of cyclone fine for catalytic gasification decreased 4-18% and 13-16%, respectively, compared to that for non-catalytic gasification. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Vapor phase oxidation of dimethyl sulfide with ozone over V2O5/TiO2 catalyst

The removal of volatile and odorous emissions from pulp and paper industrial processes usually generates secondary pollution which is treated further by scrubbing, adsorption, and catalytic incineration. Studies using a flow reactor packed with 10% vanadia/titania (V₂O₅/TiO₂) catalyst showed complete conversion of dimethyl sulfide (DMS) in the presence of ozone. The molar yields of partial oxidation products were only 10–20%. Small amounts of partial oxidation products, such as and dimethyl sulfone (DMSO₂), dimethyl disulfide (DMDS), and dimethyl sulfoxide (DMSO), were also formed. The results of the oxidation of DMS using ozone only, ozone plus catalyst, and oxygen plus catalyst suggest that the combined use of O₃ with catalyst is essential for the complete destruction of DMS to CO₂ and SO₂. A Box-Behnken design was used to determine the factors that have a significant effect on the conversion and selectivity of the products. It was concluded that product selectivity is strongly influenced by temperature, gas hourly space velocity (GHSV), and ozone concentration. The catalysts were characterized using XRD, surface area measurements, and SEM techniques. Time-on-stream studies carried out in a 500 ppmv gas stream held at 150 °C for 6 h, using 2 g of the catalyst, an ozone-to-DMS molar ratio of 0.9, and a GHSV of 37,000 h⁻¹, yielded 99.9% conversion of DMS. A plausible reaction mechanism has been proposed for the oxidation of DMS based on reaction product distribution and possible intermediates formed.     

Liquid fuel production from syngas using bifunctional CuO-CoO-Cr2O3 catalyst mixed with MFI zeolite

CuO-CoO-Cr₂O₃ mixed with MFI Zeolite (Si/Al = 35) prepared by co-precipitation was used for synthesis gas conversion to long chain hydrocarbon fuel. CuO-CoO-Cr₂O₃ catalyst was prepared by co-precipitation method using citric acid as complexant with physicochemical characterization by BET, TPR, TGA, XRD, H₂-chemisorptions, SEM and TEM techniques. The conversion experiments were carried out in a fixed bed reactor, with different temperatures (225-325 °C), gas hourly space velocity (457 to 850 h⁻¹) and pressure (28-38 atm). The key products of the reaction were analyzed by gas chromatography mass spectroscopy (GC-MS). Significantly high yields of liquid aromatic hydrocarbon products were obtained over this catalyst. Higher temperature and pressure favored the CO conversion and formation of these liquid (C₅-C₁₅) hydrocarbons. Higher selectivity of C₅ + hydrocarbons observed at lower H₂/CO ratio and GHSV of the feed gas. On the other hand high yields of methane resulted, with a decrease in C₅+ to C₁₁+ fractions at lower GHSV. Addition of MFI Zeolite (Si/Al = 35) to catalyst CuO-CoO-Cr₂O₃ resulted a high conversion of CO-hydrogenation, which may be due to its large surface area and small particle size creating more active sites. The homogeneity of various components was also helpful to enhance the synergistic effect of Co promoters.     

Mesoporous-molecular-sieve-supported Polymer Sorbents for Removing H2S from Hydrogen Gas Streams

A series of sorbents with a linear polyethylenimine (PEI) supported on the mesoporous molecular sieves, including MCM-41, MCM-48 and SBA-15, have been prepared and used to remove H₂S from a model gas containing 0.40 v% of H₂S and 20 v% H₂ in N₂ gas. The sorption was conducted in a fixed-bed system at a temperature range of 22–75 °C, a GHSV range of 337–1,011 h^?1 and atmospheric pressure. The effects of the operating temperature, GHSV, the amount of PEI loading and the different molecular sieve supports were studied. A reduction in the temperature and GHSV improves the sorption performance of the supported PEI sorbents. A synergetic effect of the SBA?15 support and PEI on the H₂S sorption performance was observed. Loading 50 wt% PEI on SBA-15 gave the best breakthrough capacity, while loading 65 wt% PEI on SBA-15 had the highest saturation capacity. The mesoporous molecular sieve with large pore size and three-dimensional channel structure favors increasing the kinetic capacity of the supported PEI sorbent. In addition, the developed sorbents can be regenerated easily at mild conditions (temperature range of 75–100 °C) and have excellent regenerability and stability. The results indicate that the mesoporous-molecular-sieve-supported polymer sorbents are promising for removing H₂S from hydrogen gas streams.     

The phenol steam reforming reaction towards H2 production on natural calcite

The steam reforming of phenol towards H₂ production was studied in the 650–800 °C range over a natural pre-calcined (air, 850 °C) calcite material. The effects of reaction temperature, water, hydrogen, and carbon dioxide feed concentrations, and gas hourly space velocity (GHSV, h⁻¹) were investigated. The increase of reaction temperature in the 650–800 °C range and water feed concentration in the 40–50 vol% range were found to be beneficial for catalyst activity and H₂-yield. A similar result was also obtained in the case of decreasing the GHSV from 85,000 to 30,000 h⁻¹. The effect of concentration of carbon dioxide and hydrogen in the phenol/water feed stream was found to significantly decrease the rate of phenol steam reforming reaction. The latter was probed to be related to the reduction in the rate of water dissociation as evidenced by the significant decrease in the concentration of adsorbed bicarbonate and OH species on the surface of CaO according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)-CO₂ adsorption experiments in the presence of water and hydrogen in the feed stream. Details of the CO₂ adsorption on the CaO surface at different reaction temperatures and gas atmospheres using in situ DRIFTS and transient isothermal adsorption experiments with mass spectrometry were obtained. Bridged, bicarbonate and unidentate carbonate species were formed under CO₂/H₂O/He gas mixtures at 600 °C with the latter being the most populated. A substantial decrease in the surface concentration of bicarbonate and OH species was observed when the CaO surface was exposed to CO₂/H₂O/H₂/He gas mixtures at 600 °C, result that probes for the inhibiting effect of H₂ on the phenol steam reforming activity. Phenol steam reforming reaction followed by isothermal oxygen titration allowed the measurement of accumulated “carbonaceous” species formed during phenol steam reforming as a function of reaction temperature and short time on stream. An increase in the amount of “carbonaceous” species with reaction time (650–800 °C range) was evidenced, in particular at 800 °C (4.7 vs. 6.7 mg C/g solid after 5 and 20 min on stream, respectively).     

The deactivating effect of carbon dioxide on iron-oxide catalyst in the dehydrogenation of methylbutenes

Characteristics of the most energy-intensive second stage of the two-stage production of isoprene from isopentane, i.e., dehydrogenation of methylbutenes are studied to improve the technical and economic performance of the process. The effect of the carbon dioxide formed during self-regeneration of the ironoxide catalyst (according to the reaction C_coke + 2H₂O → 2H₂ + CO₂) on the conversion of methylbutenes and selectivity with respect to isoprene is investigated. It is found that the presence of CO₂ in the reaction batch has a considerable effect on the conversion of methylbutenes; when the content of CO₂ in the raw material feed is 1.5 wt %, conversion of methylbutenes is reduced by 5–6%. It is demonstrated that CO₂ reversibly deactivates the catalyst and the catalyst activity is restored when its influx is discontined (the yield of isoprene returns gradually to its original value). The recovery rate depends on the concentration and duration of exposure to carbon dioxide. Treatment of the catalyst by steam in the absence of the reaction mixture leads to rapid regeneration of the catalyst. It is concluded that measures to continuously monitor CO₂ in the contact gas during the first stage of dehydrogenation, and to select the optimum modes (temperature, steam/raw materials ratio, etc.) for reducing carbon residue during the operation of iron-oxide catalyst in order to implement the two-stage technology for the dehydrogenation of methylbutenes (the main goal of which is to raise the conversion of methylbutenes to 35–40%) are of special importance.