Electrocatalytic CO_(2)reduction to syngas

While carbon dioxide(CO_(2))is a major greenhouse gas,it is also an important C1 resource.In the trend of energy conservation and emission reduction,electrocatalytic reduction has become a very promising strategy for CO_(2)utilization because it can convert CO_(2)directly to high-valued chemicals and fuels under mild conditions.In particular,the product CO and by-product H_(2)can be combined into syngas by an electrocatalytic CO_(2)reduction reaction(CO_(2)RR)in an aqueous medium.Different molar ratios of CO and H_(2)may be used to produce essential bulk chemicals or liquid fuels such as methanol,alkanes,and olefins through thermochemical catalysis,Fischer-Tropsch synthesis,microbial fermentation,and other techniques.This work discusses the latest strategies in controlling the molar ratio of CO/H_(2)and improving the yield of CO_(2)RR-to-syngas.The challenges of electrocatalytic syngas production are analyzed from an industrial application perspective,and the possible measures to overcome them are proposed in terms of new catalyst design,electrolyte innovation,flow reactor optimization,anodic reaction coupling,and operando technique application.

Influence of syngas components and ash particles on the radiative heat transfer in a radiant syngas cooler

Radiant syngas cooler(RSC)is widely used as a waste heat recovery equipment in industrial gasification.In this work,an RSC with radiation screens is established and the impact of gaseous radiative property models,gas components,and ash particles on heat transfer is investigated by the numerical simulation method.Considering the syngas components and the pressure environment of the RSC,a modified weighted-sum-of-gray-gases model was developed.The modified model shows high accuracy in validation.In computational fluid dynamics simulation,the calculated steam production is only 0.63%in error with the industrial data.Compared with Smith's model,the temperature decay along the axial direction calculated by the modified model is faster.Syngas components are of great significance to heat recovery capacity,especially when the absorbing gas fraction is less than 10%.After considering the influence of particles,the outlet temperature and the proportion of radiative heat transfer are less affected,but the difference in steam output reaches 2.7 t·h^(-1).The particle deposition on the wall greatly reduces the heat recovery performance of an RSC.

Manipulating photogenerated electron flow in nickel single‐atom catalysts for photocatalytic CO_(2) reduction into tunable syngas

The key to designing photocatalysts is to orient the migration of photogenerated electrons to the target active sites rather than dissipate at inert sites.Herein,we demonstrate that the doping of phosphorus(P)significantly enriches photogenerated electrons at Ni active sites and enhances the performance for CO_(2) reduction into syngas.During photocatalytic CO_(2) reduction,Ni single‐atom‐anchored P‐modulated carbon nitride showed an impressive syngas yield rate of 85μmol gcat^(−1)h^(−1) and continuously adjustable CO/H_(2) ratios ranging from 5:1 to 1:2,which exceeded those of most of the reported carbon nitride‐based single‐atom catalysts.Mechanistic studies reveal that P doping improves the conductivity of catalysts,which promotes photogenerated electron transfer to the Ni active sites rather than dissipate randomly at low‐activity nonmetallic sites,facilitating the CO_(2)‐to‐syngas photoreduction process.

MOF‐derived 1D/3D N‐doped porous carbon for spatially confined electrochemical CO_(2) reduction to adjustable syngas

Electrochemical reduction of CO_(2) to syngas(CO and H_(2))offers an efficient way to mitigate carbon emissions and store intermittent renewable energy in chemicals.Herein,the hierarchical one‐dimensional/three‐dimensional nitrogen‐doped porous carbon(1D/3D NPC)is prepared by carbonizing the composite of Zn‐MOF‐74 crystals in situ grown on a commercial melamine sponge(MS),for electrochemical CO_(2) reduction reaction(CO_(2)RR).The 1D/3D NPC exhibits a high CO/H_(2) ratio(5.06)and CO yield(31 mmol g^(−1)h^(−1))at−0.55 V,which are 13.7 times and 21.4 times those of 1D porous carbon(derived from Zn‐MOF‐74)and N‐doped carbon(carbonized by MS),respectively.This is attributed to the unique spatial environment of 1D/3D NPC,which increases the adsorption capacity of CO_(2) and promotes electron transfer from the 3D N‐doped carbon framework to 1D carbon,improving the reaction kinetics of CO_(2)RR.Experimental results and charge density difference plots indicate that the active site of CO_(2)RR is the positively charged carbon atom adjacent to graphitic N on 1D carbon and the active site of HER is the pyridinic N on 1D carbon.The presence of pyridinic N and pyrrolic N reduces the number of electron transfer,decreasing the reaction kinetics and the activity of CO_(2)RR.The CO/H_(2) ratio is related to the distribution of N species and the specific surface area,which are determined by the degree of spatial confinement effect.The CO/H_(2) ratios can be regulated by adjusting the carbonization temperature to adjust the degree of spatial confinement effect.Given the low cost of feedstock and easy strategy,1D/3D NPC catalysts have great potential for industrial application.

Comparative Study of Exhaust Emissions from Diesel and Syngas Powered 3.5 kW Compression Ignition Engine with and without Load

Despite diesel engines being highly efficient, with low fuel consumption and reduced carbon dioxide emissions, they emit relatively high levels of particulate matter and oxides of nitrogen (NOx) due to high exhaust gas temperatures. Engine emissions show the quality and completeness of combustion. This paper aims to present the results of a study comparing exhaust emissions from a diesel and syngas powered engine. Syngas was produced from co-firing coal and biomass in a gasifier then cleaned, cooled and applied as an alternative fuel in an engine operated from 0 - 100% load. Exhaust-emissions were monitored at this load conditions. The exhaust-temperature was measured using thermocouples and the emission gases were analyzed using Testo 350. The emissions were lower and decreased as the engine load increased, except for sulphur dioxide and NOx. The study shows that levels of carbon monoxide, were higher in a range of 46.5 - 80.2%, while carbon dioxide was 3.3 - 18% higher compared to those from diesel. Hydrocarbon emissions were 480 and 1250 ppm for diesel and syngas respectively. The study reveals that the engine operates optimally at higher loads since hydrocarbons and oxides of carbon are low due to complete combustion at higher temperatures. Exhaust gas temperature was higher in the syngas fuel and increased as the engine load increased in the range of 455.83 - 480.03˚C which influenced the formation of NOx. NOx from diesel was found to be higher, ranging from 32.5 - 40.5%, compared to those from syngas with an engine load of 75%. The study observed that relative to diesel, the emissions of sulfur dioxide at 50% engine load were lower in a range of 23.7 - 57.1%. Emissions of hydrocarbons depended on the degree of substitution of diesel and engine load. The study therefore shows that, relative to diesel, emissions decreased when syngas was used with upgraded syngas from Prosporis juliflora presenting as the best alternative followed by Hyphanae compressa, and lastly rice husk. For optimal performance of the syngas fuelled engine, the study reports that the engine should be operated at engine loads above 50% with strategies on NOx emissions considered.

Selective oxidation of methane to syngas using Pr_(0.7)Zr_(0.3)O_(2-δ): Stability of oxygen carrier

Pr0.7Zr0.3O2-δ solid solution was prepared by co-precipitation method and used as an oxygen carrier in the selective oxidation of methane to syngas(methane/air redox process). The evolution on the physicochemical properties of Pr0.7Zr0.3O2-δ during the redox process was studied by means of X-ray diffraction(XRD), H2 temperature-programmed reduction(H2-TPR), O2temperature-programmed desorption(O2-TPD), Brunauer-Emmett-Teller(BET) surface area measurement and X-ray photoelectron spectroscopy(XPS) technologies. The results indicated that Pr0.7Zr0.3O2-δ solid solution showed the high activity for the methane conversion to syngas with a high CO selectivity in the range of 83.5%-88.1%. Though Pr-Zr solid solution possessed high thermal stability, lattice oxygen was obviously reduced for the recycled sample due to decreased surface oxygen which promoted oxygen vacancies. The increased oxygen vacancies seemed to enhance the oxygen transfer ability in the redox process and provided sufficient oxygen for the methane selective oxidation, resulting in a satisfactory activity. The problem of hot pot was avoided by comparing fresh, aged and recycle sample in the reaction.

Bio-methanol from Bio-oil Reforming Syngas Using Dual-reactor

A dual-reactor, assembled with the on-line syngas conditioning and methanol synthesis, was successfully applied for high efficient conversion of rich CO2 bio-oil derived syngas to bio-methanol. In the forepart catalyst bed reactor, the catalytic conversion can effectively adjust the rich-CO2 crude bio-syngas into the CO-containing bio-syngas using the CuZnA1Zr catalyst. After the on-line syngas conditioning at 450℃, the CO2/CO ratio in the blo- syngas significantly decreased from 6.3 to 1.2. In the rearward catalyst bed reactor, the conversion of the conditioned bio-syngas to bio-methanol shows the maximum yield about 1.21 kg/（kgcatarh） MeOH with a methanol selectivity of 97.9% at 260 ~C and 5.05 MPa using conventional CuZnA1 catalyst, which is close to the level typically obtained in the conventional methanol synthesis process using natural gas. The influences of temperature, pressure and space velocity on the bio-methanol synthesis were also investigated in detail.

Syngas Production by Methane Reforming with Carbon Dioxide on Noble Metal Catalysts

A series of noble metal catalysts （Ru, Rh, Ir, Pt, and Pd） supported on alumina-stabilized magnesia （Spinel） were used to produce syngas by methane reforming with carbon dioxide. The synthesized catalysts were characterized using BET, TPR, TPO, TPH, and H2S chemisorption techniques. The activity results showed high activity and stability for the Ru and Rh catalysts. The TPO and TPH analyses indicated that the main reason for lower activity and stability of the Pd catalyst was the formation of the less reactive deposited carbon and sintering of the catalyst.

Methanation of syngas over coral reef-like Ni/Al_2O_3 catalysts

Coral reef-like Ni/Al2O3 catalysts were prepared by co-precipitation of nickel acetate and aluminium nitrate with sodium carbonate aqueous solution in the medium of ethylene glycolye.Methanation of syngas was carried out over coral reef-like Ni/Al2O3 catalysts in a continuous flow type fixed-bed reactor.The structure and properties of the fresh and used catalysts were studied by SEM,N2 adsorption-desorption,XRD,H2-TPR,O2-TPO,TG and ICP-AES techniques.The results showed that the coral reef-like Ni/Al2O3 catalysts exhibited better activity than the conventional Ni/Al2O3-H2O catalysts.The activities of coral reef-like catalysts were in the order of Ni/Al2O3-673Ni/Al2O3-573Ni/Al2O3- 473Ni/Al2O3-773.Ni/Al2O3-673-EG catalyst showed not only good activity and improved stability but also superior resistance to carbon deposition,sintering,and Ni loss.Under the reaction conditions of CO/H2（molar ratio）=1：3,593 K,atmospheric pressure and a GHSV of 2500 h-1,CH4 selectivity was 84.7%,and the CO conversion reached 98.2%.

Ni/Al_2O_3 catalysts for syngas methanation: Effect of Mn promoter

Ni/Al2O3 catalysts with different amounts of manganese ranging from 1 to 3 wt% as promoter were prepared by co-impregnation method. The catalysts were characterized by N2 physisorption, XRD, TPR, SEM and TEM. Their catalytic activity towards syngas methanation reaction was also investigated using a fixed-bed integral reactor. It was demonstrated that the addition of manganese to Ni/Al2O3 catalysts can increase the catalyst surface area and average pore volume, but decrease NiO crystallite size, leading to higher activity and stability. The effects of reaction temperature, pressure and weight hourly space velocity （WHSV） on carbon oxides conversion and CH4 formation rate were also studied. High carbon oxides conversion, CH4 selectivity and formation rate were achieved at the reaction temperature range of 280 300℃.

Alkylation Activity of Benzene with Syngas over Cu-based Catalysts

A series of Cu-based catalysts were developed for alkylation of benzene with syngas. The catalyst samples were prepared by the impregnation method, and were characterized by XRD, XRF, NH3-TPD, and TEM and evaluated in a fixed bed reactor. The optimized reaction temperature of Cu/Al2O3/ZSM-5 catalyst was 350 ℃, while higher contents of copper were conducive to alkylation of benzene with syngas. The new medium strength acid centers in the catalyst created by Cu were beneficial to alkylation. Hydrogenation reaction of CO was executed on the metal centers without dissociation, Dimethyl ether(DME) was the major intermediate over Cu-based catalysts. Higher selectivity of methylation and lower selectivity of heavy aromatics were confirmed after the second metal(Zn, Mn, or V) was added to the copper catalyst. Cu was partly covered by Zn in the Cu-Zn/Al2O3/ZSM-5 catalyst leading to low dispersion and low activity of copper. Cu-Mn/Al2O3/ZSM-5 catalyst possessed the best yield of methylation product. Cu-Mn composite oxides were probably formed in fresh catalyst, which blocked the sintering of Cu in the reaction process. The loading of Cu decreased dramatically after the introduction of V, while causing an increase of the amount of medium strength acid centers at the same time. V prevented the sintering of copper particles during the reducing process and had a promoting effect on the activity of Cu.

Selective conversion of syngas to propane over ZnCrO_x-SSZ-39 OX-ZEO catalysts

Oxide-Zeolite(OX-ZEO) bifunctional catalyst design concept has been exemplified in several processes to direct conversion syngas to value-added chemicals and fuels such as mixed light olefins, ethylene, aromatics and gasoline.Herein we demonstrate that the product can be steered toward liquefied petroleum gas(LPG) with a selectivity up to 89% in hydrocarbons especially propane selectivity reaching 80% at CO conversion of 63% using ZnCrOx-H-SSZ-39 catalyst.Interestingly, the quantity of the acid sites of SSZ-39 does not influence obviously the hydrocarbon distribution but the strength is crucial for selective formation of propane.This finding provides an alternative route of LPG synthesis from a variety of carbon resources via syngas.

Cu-Co bi-metal catalyst prepared by perovskite CuO/LaCoO_3 used for higher alcohol synthesis from syngas

Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO3 particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified C02C species.

Comparative study of fluidized-bed and fixed-bed reactor for syngas methanation over Ni-W/TiO_2-SiO_2 catalyst

In this work,syngas methanation over Ni-W/TiO2-SiO2catalyst was studied in a fluidized-bed reactor(FBR)and its performance was compared with a fixed-bed reactor(FIXBR).The effects of main operating variables including feedstock gases space velocity,coke content,bed temperature and sulfur-tolerant stability of 100 h life were investigated.The structure of the catalysts was characterized by XRD,N2adsorptiondesorption and TEM.It is found that under same space velocity from 5000 h 1to 25000 h 1FBR gave a higher CH4yield,lower coke content,and lower bed temperature than those obtained in FIXBR.Ni-W/TiO2-SiO2catalyst possessed excellent sulfur-tolerant stability on the feedstock gases less than 500 ppm H2S in FBR.The carbon deposits formed on the spent catalyst were in the form of carbon fibers in FBR,while in the form of dense accumulation distribution appearance in FIXBR.

Nanosheet-structured K–Co–MoS_2 catalyst for the higher alcohol synthesis from syngas: Synthesis and activation

The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.

Hydrogen and syngas production from two-step steam reforming of methane using CeO_2 as oxygen carrier

CeO2 oxygen carrier was prepared by precipitation method and tested by two-step steam reforming of methane （SRM）. Two-step SRM for hydrogen and syngas generation is investigated in a fixed-bed reactor. Methane is directly converted to syngas at a H2/CO ratio close to 2 ： 1 at a high temperature （above 750 °C） by the lattice oxygen of CeO2; methane cracking is found when the reduction degree of CeO2 was above 5.0% at 850 °C in methane isothermal reaction. CeO2？δ obtained from methane isothermal reaction can split water to generate CO-free hydrogen and renew its lattice oxygen at 700 °C; simultaneously, deposited carbon is selectively oxidized to CO2 by steam following the reaction （C＋2H2O→CO2＋2H2）. Slight deactivation in terms of amounts of desired products （syngas and hydrogen） is observed in ten repetitive two-step SRM process due to the carbon deposition on CeO2 surface as well as sintering of CeO2.

Ni catalysts supported on nanocrystalline magnesium oxide for syngas production by CO_2 reforming of CH_4

CO2 reforming of methane （CDRM） was carried out over MgO supported Ni catalysts with various Ni loadings. The preparation of MgO supported Ni catalysts via surfactant-assisted precipitation method led to the formation of a nanocrystalline carrier for nickel catalysts. The synthesized samples were characterized by XRD, N2 adsorption-desorption, H2 chemisorption, TPR, TPO and SEM techniques. It was found that the high catalytic activity and stability of the prepared catalysts could be attributable to high dispersion of reduced Ni species and basicity of support surface. In addition, the effect of feed ratio, nickel loading and GHSV on the catalytic performance of CDRM over the catalysts were investigated.

Production of hydrogen and syngas via pyrolysis of bagasse in a dual bed reactor

Pyrolysis of bagasse followed by thermal cracking of tar was carded out at atmospheric pressure using a dual bed reactor. The first bed was used for the pyrolysis and the second bed was used for thermal cracking of tar. Iron fillings were used as the packed bed material in the second bed. The effects of reaction time （20 to 40 rain）, reactor temperature （600 to 900 ℃） and packed bed height （40-100 mm） on the product （char, tar and gas） yield and gas （H2, CO, CO2, CH4, CnHm） composition were studied. Over the ranges of the experimental conditions used, the operating conditions were optimized for pyrolysis temperature around 850 ℃, a reaction time of 30 min and packed bed height of 100 mm, thus we could obtain a gas richer in hydrogen and carbon monoxide and poorer in carbon dioxide and hydrocarbons. It was observed that compared with single bed process, dual bed process increased the gas yield from 0.397 to 0.750 m3/kg and decreased the tar yield from 0.445 to 0.268 g/g while the heating value of the product gas remained almost constant （10-11 M J/m3）.

Intrinsic Kinetics of Dimethyl Ether Synthesis from Syngas

The intrinsic kinetics of dimethyl ether (DME) synthesis from syngas over amethanol synthesis catalyst mixed with methanol dehydration catalyst has been investigated in atubular integral reactor at 3-7 MPa and 220-260℃. The three reactions including methanol synthesisfrom CO and H_2, CO_2 and H_2, and methanol dehydration were chosen as the independent reactions.The L-H kinetic model was presented for dimethyl ether synthesis and the parameters of the modelwere obtained by using simplex method combined with genetic algorithm. The model is reliableaccording to statistical analysis and residual error analysis. The synergy effect of the reactionsover the bifunctional catalyst was compared with the effect for methanol synthesis catalyst underthe same conditions based on the model. The effects of syngas containing Na on the reactions werealso simulated.

Partial Oxidation of Methane to Syngas over Monolithic Ni/γ-Al_2O_3 Catalyst——Effects of Rare Earths and Other Basic Promoters

A series of monolithic Ni/γ-Al2O3 catalysts with and without basic promoters （Na, Sr, La, Ce） were prepared. Partial oxidation of methane （POM） to syngas was carried out in a continuous-flow, fixed-bed reactor. The influences of reaction conditions, including temperature, CH4/O2 ratio and space velocity, on the performance of the catalyst were investigated. The results show that at a high space velocity of 1 ×10^5 h^-1, optimal CH4 conversion can be obtained. Effects of promoters such as Na, Sr, Ce, La were also investigated, and the catalyst samples were characterized by means of temperature-programmed reduction and XRD techniques. XRD suggests that the addition of promoters has no influence on the crystal structure of Ni/γ-Al2O3 catalyst. The results show that the addition of a small amount of promoters improves the reducibility and activity of the catalyst. The side reaction CH4 ＋ 2O2→CO2 ＋ H2O, is fully restrained and 100% H2 selectivity is achieved when Ce and La are used as promoters, respectively.