Hydrogen production by steam reforming of LPG using supported perovskite type precursors

Perovskites supported on Al₂O₃ (LaNi/AL) and CeO₂–SiO₂ (LaNi/CS) were tested as catalyst precursors for steam reforming of liquefied petroleum gas (SRLPG). The role of different supports in perovskites-derived catalysts performances was evaluated. A non-supported LaNiO₃ (LaNi) was also synthesized for comparison. According to the in-situ X-Ray Diffraction analyses, a reduction temperature of 700 °C was enough to generate Ni⁰ and La₂O₃, except for LaNi/AL. X-ray absorption Near Edge Spectroscopy (XANES) showed a direct influence of the supports on the reducibility of the samples. At 600 °C, the supported precursors LaNi/AL and LaNi/CS were more stable than LaNi during the SRLPG reaction. The alumina support provided a higher activity to LaNi/AL mainly due to the strong metal-support interaction. At 700 °C, the LPG conversion of LaNi/CS was near 100%. At both temperatures, the lowest carbon accumulation rate was obtained by LaNi/CS likely due to ceria oxygen mobility.     

Vanadium promoted Ni(Mg,Al)O hydrotalcite-derived catalysts for CO2 methanation

A series of V-promoted hydrotalcite-derived nickel catalysts (1.0, 2.0, and 4.0 wt%) were tested in CO₂ methanation. Ni–I–V2.0 with 2.0 wt% vanadium loading showed the highest catalytic activity, achieving 74.7% of CO₂ conversion and 100% of CH₄ selectivity at 300 °C. XRD and XANES analyses showed that the smallest Ni⁰ particles in Ni–I–V2.0 were consistent with the improved textural features observed for this catalyst. Moreover, CO₂-TPD revealed the highest sum of weak and medium basic sites in Ni–I–V2.0 that can positively influence catalytic behavior. For the studied catalysts, a clear correlation was demonstrated between the catalytic activity and specific surface area, as well as the basic properties.     

Reforming of a model sulfur-free biogas on Ni catalysts supported on Mg(Al)O derived from hydrotalcite precursors: Effect of La and Rh addition

Ni catalysts supported on calcined Mg–Al hydrotalcite, Mg(Al)O, were prepared and the effect of the addition of La and/or Rh was tested in the performance of the catalysts in the dry reforming of methane with excess of methane in the feed, simulating a model sulfur-free biogas. The effect of adding synthetic air was assessed. The catalysts were characterized by surface area (BET), XRD, TPR and XPD. The results showed the reconstruction of the hydrotalcite structure during the Ni(NO₃) impregnation, with the segregation of the lanthanum. In the catalyst without Rh and La, Ni showed a strong interaction with the support Mg(Al)O, showing high reduction temperatures in TPR test. The addition of Rh and La increased the amount of reducible Ni species and facilitated the reduction of the species interacting strongly with the support which resulted in high rates of carbon deposition. The NiMgAl catalyst presented the strong Ni-support interactions and the best performance with low carbon deposition at both conditions of reaction. The NiMgAl catalyst did not present deactivation during 24 h of stability testing in the oxidative reforming of a model biogas.     

LPG发动机混合器结构尺寸的计算

本文对燃用LPG（液化石油气）发动机的混合器结构尺寸进行了详细的计算，给出了混合器喉管直径的计算公式，为混合器的设计制造提供了理论依据，结果表明，所制造的混合器与发动机可以很好地匹配。     

Development of highly effective supported nickel catalysts for pre-reforming of liquefied petroleum gas under low steam to carbon molar ratios

The pre-reforming of commercial liquefied petroleum gas (LPG) was investigated over Ni–CeO₂ catalysts at low steam to carbon (S/C) molar ratios less than 1.0. It was found that the catalytic activity and selectivity depended strongly on the nature of the support and the interaction between Ni and CeO₂. The Ni–CeO₂/Al₂O₃ catalysts, which were prepared by impregnating boehmite (AlOOH) with an aqueous solution of cerium and nickel nitrates, exhibited the optimal catalytic activity and remarkable stability for the steam reforming of LPG in the temperature range of 275–375 °C. The effects of CeO₂ loading, reaction temperature and S/C ratio on the catalytic behavior of the Ni–CeO₂/Al₂O₃ catalysts were discussed in detail. The results showed that the catalysts with 10 wt.% CeO₂ had the highest catalytic activity, and higher S/C ratios contributed to LPG reforming and the methanation of carbon oxides and hydrogen. The XRD and H₂-TPR analyses revealed that the strong interaction between Ni and CeO₂ resulted in the formation of CeAlO₃ in the Ni–CeO₂/Al₂O₃ catalysts reduced. The stability tests of 15Ni–10CeO₂/Al₂O₃ catalyst at 350 °C indicated that the catalyst was stable, and the stability could be enhanced by increasing S/C ratio.     

Tailored Ce- and Zr-doped Ni/hydrotalcite materials for superior sorption-enhanced steam methane reforming

Multi-functional hybrid materials are attractive for producing high-purity hydrogen (H₂) via catalytic steam reforming coupled with low temperature adsorptive separation of CO₂. In this work, modified Ni/hydrotalcite-like (HTlc) hybrid materials promoted with Ce and Zr species were synthesized and applied for the sorption-enhanced steam methane reforming process (or SESMR). The promotion with Ce and Zr resulted in strongly basic sites for CO₂ adsorption, and hence, improved H₂ production. Especially, the Ce-promoted hybrid material (Ce-HM1) exhibited the highest adsorption capacity (1.41 mol CO₂/kg sorbent), producing 97.1 mol% H₂ at T = 723 K, P = 0.1 MPa, S/C = 4.5 mol/mol and gas hourly space velocity or GHSV = 3600 mL/(g h); the breakthrough time was 1 h. High surface area and basicity of the promoted materials inhibited coke formation and undesired reactions. In addition to the improved catalytic activity and adsorption characteristics, these materials were stable and easily regenerable. Multi-cycle durability tests revealed that both the promoted materials Ce-HM1 and Zr-HM1 remained stable for up to 13 and 17 cycles. In contrast, the unpromoted hybrid material (HM1) was stable for 9 cycles only. Thus, promotion with Ce and Zr was beneficial for producing pure H₂.     

Hydrogen production by methane decomposition: A comparative study of supported and bulk ex-hydrotalcite mixed oxide catalysts with Ni,Mg and Al

A catalytic comparative study of CO_x-free hydrogen production by methane decomposition was carried out. Catalytic performances of bulk Ni-mixed oxides derived from Ni/Mg/Al-hydrotalcites (ex-HTs-Ni) were compared with those obtained with Ni supported on mixed oxides derived from Mg/Al-hydrotalcites (Ni/ex-HTs), or on commercial supports (γ-Al₂O₃, MgO and MgO-modified γ-Al₂O₃). Catalyst characterization and their catalytic performance showed both ex-HTs-Ni and Ni/ex-HTs appear to be a similar regardless of their method of preparation. Ni/γ-Al₂O₃ was the best supported catalyst, although the catalytic performances of the ex-HTs catalysts were better. Higher NiMg interaction in ex-HTs provides higher resistance to deactivation. Characterization by TG, Raman spectroscopy and TEM of spent catalysts in the reaction suggest the degree of ordering of the graphitic layers of the carbon deposit onto the catalyst surface is the key factor in the catalyst deactivation. The higher degree of ordering or graphitization of the carbon produced with the higher concentration of sp2 carbons on the surface of the Ni/γ-Al₂O₃ favours its faster deactivation by Ni-coverage than the bulk catalyst (ex-HT-Ni), in which the MWNT type carbon is mainly obtained.     

Improving the performance of dual fuel engines running on natural gas/LPG by using pilot fuel derived from jojoba seeds

The use of jojoba methyl ester as a pilot fuel was investigated for almost the first time as a way to improve the performance of dual fuel engine running on natural gas or liquefied petroleum gas (LPG) at part load. The dual fuel engine used was Ricardo E6 variable compression diesel engine and it used either compressed natural gas (CNG) or LPG as the main fuel and jojoba methyl ester as a pilot fuel. Diesel fuel was used as a reference fuel for the dual fuel engine results. During the experimental tests, the following have been measured: engine efficiency in terms of specific fuel consumption, brake power output, combustion noise in terms of maximum pressure rise rate and maximum pressure, exhaust emissions in terms of carbon monoxide and hydrocarbons, knocking limits in terms of maximum torque at onset of knocking, and cyclic variability data of 100 engine cycles in terms of maximum pressure and its pressure rise rate average and standard deviation. The tests examined the following engine parameters: gaseous fuel type, engine speed and load, pilot fuel injection timing, pilot fuel mass and compression ratio. Results showed that using the jojoba fuel with its improved properties has improved the dual fuel engine performance, reduced the combustion noise, extended knocking limits and reduced the cyclic variability of the combustion.     

在电喷发动机上燃用LPG的试验研究

我国的LPG中C4H10(丁烷)含量比较大。在电喷发动机上使用汽油、纯C，H8(丙烷)和75％C3H8 25％C4H10三种燃料进行对比试验。当用纯C3H8代替汽油时发动机功率下降10％，但有害排放物下降5090％。在LPG中当提高C4H10的比例为25％时，发动机功率下降幅度减少，同时有害排放物可继续下降。在我国作为清洁燃料，LPG在电喷发动机上的应用具有广阔的前景。     

Effect of calcination temperature of mesoporous alumina xerogel (AX) supports on hydrogen production by steam reforming of liquefied natural gas (LNG) over Ni/AX catalysts

Mesoporous alumina xerogel (AX) supports prepared by a sol–gel method were calcined at various temperatures. Ni/mesoporous alumina xerogel (Ni/AX) catalysts were then prepared by an impregnation method, and were applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of calcination temperature of AX supports on the catalytic performance of Ni/AX catalysts in the steam reforming of LNG was investigated. Physical and chemical properties of AX supports and Ni/AX catalysts were strongly influenced by the calcination temperature of AX supports. Crystalline structure of AX supports was transformed in the sequence of γ-alumina → (γ + θ)-alumina → θ-alumina → (θ + α)-alumina with increasing calcination temperature from 700 to 1000 °C. Nickel species were strongly bonded to the divalent vacancy of γ-alumina, (γ + θ)-alumina, and θ-alumina through the formation of nickel aluminate phase. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to calcination temperature of AX supports. Among the catalysts tested, Ni/AX-900 (nickel catalyst supported on AX that had been calcined at 900 °C) showed the best catalytic performance. The smallest nickel crystalline size and the strongest nickel–alumina interaction were responsible for high catalytic performance of Ni/AX-900 catalyst in the steam reforming of LNG.     

Hydrogen production by catalytic partial oxidation of methane and propane on Ni and Pt catalysts

In recent years the catalytic partial oxidation has been taken into consideration as a suitable process for hydrogen production, because of its exothermic nature which makes the process less energy and capital cost intensive with respect to steam reforming. In this paper the behaviour of three different catalyst typologies, two based on Ni–_Al2O3${\mathrm{Al}}_2{\mathrm{O}}_3$ (different in active phase composition) and one constituted by Pt supported on _CeO2${\mathrm{CeO}}_2$, is studied for partial oxidation of propane (as representative of liquefied petroleum gas). For comparison the same catalysts have been tested also in methane partial oxidation.     

Effect of SiO2-ZrO2 supports prepared by a grafting method on hydrogen production by steam reforming of liquefied natural gas over Ni/SiO2-ZrO2 catalysts

SiO₂-ZrO₂ supports with various zirconium contents are prepared by grafting a zirconium precursor onto the surface of commercial Carbosil silica. Ni(20 wt.%)/SiO₂-ZrO₂ catalysts are then prepared by an impregnation method, and are applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of SiO₂-ZrO₂ supports on the performance of the Ni(20 wt.%)/SiO₂-ZrO₂ catalysts is investigated. SiO₂-ZrO₂ prepared by a grafting method serves as an efficient support for the nickel catalyst in the steam reforming of LNG. Zirconia enhances the resistance of silica to steam significantly and increases the interaction between nickel and the support, and furthermore, prevents the growth of nickel oxide species during the calcination process through the formation of a ZrO₂-SiO₂ composite structure. The crystalline structures and catalytic activities of the Ni(20 wt.%)/SiO₂-ZrO₂ catalysts are strongly influenced by the amount of zirconium grafted. The conversion of LNG and the yield of hydrogen show volcano-shaped curves with respect to zirconium content. Among the catalysts tested, the Ni(20 wt.%)/SiO₂-ZrO₂ (Zr/Si = 0.54) sample shows the best catalytic performance in terms of both LNG conversion and hydrogen yield. The well-developed and pure tetragonal phase of ZrO₂-SiO₂ (Zr/Si = 0.54) appears to play an important role in the adsorption of steam and subsequent spillover of steam from the support to the active nickel. The small particle size of the metallic nickel in the Ni(20 wt.%)/SiO₂-ZrO₂ (Zr/Si = 0.54) catalyst is also responsible for its high performance.     

Ni based catalysts promoted with cerium used in the steam reforming of toluene for hydrogen production

Ni_xMg_6?xAl_1.8Ce_0.2 (with 0 ≤ x ≤ 6) mixed oxides catalysts were prepared by hydrotalcite route. All the oxides were calcined at 800 °C and characterized by different physico-chemical methods. The catalysts are then reduced before their use in the steam reforming of toluene. The XRD and TG/DTA confirmed the formation of the hydrotalcite structure for the non-calcined samples. The N₂ adsorption/desorption results revealed that all catalysts correspond to mesoporous materials. The study by temperature programmed reduction (H₂-TPR) showed that the reducibility of the catalysts is influenced by the nickel content. The CO₂-TPD results showed that the catalyst with high magnesium content present the highest basicity. The Ni₂Mg₄Al_1.8Ce_0.2 shows the best toluene conversion among all the catalysts and it was then compared to a non-promoted catalyst. The spent catalysts were characterized by TPO, TG/DTA and XRD and they didn't reveal any coke formation.     

Hydrogen production by steam reforming of acetic acid using hydrotalcite type precursors

Acetic acid can be used as a model compound in the study of the steam reforming of the hydrophilic phase of bio-oil. In order to perform acetic acid reforming reactions, low cost catalysts with high catalytic activity and selectivity are required. Thus, NiMgAl hydrotalcite derived catalysts emerge as a good alternative. In this work, four NiMgAl hydrotalcite type precursors were prepared, with different Ni/Mg molar ratios (0.3, 0.4, 0.5, and 0.6). Various characterization tests have been performed for the prepared hydrotalcite type precursors. The stability of the catalytic activity was evaluated during 24 h and the used samples were submitted to a thermogravimetric analysis to evaluate carbon accumulation. Characterization tests proved that Ni/Mg ratios had a direct influence in the reducibility of the precursors. The Temperature-programmed surface reaction analysis showed that the steam reforming of acetic acid occurred majorly when the temperature reached 873 K. Stability test showed that precursors 04NiMg and 05NiMg had the best catalytic performance. It was also seen that sample 06NiMg suffered from deactivation by carbon deposition, which was confirmed by the thermogravimetric analysis.     

DME/LPG燃料比例实时优化的HCCI燃烧控制新方法

根据燃料设计的思想,提出了混合燃料比例实时优化的HCCI燃烧控制新方法。在一台2135柴油机上,通过燃料成分设计（DME／LPG混合燃料）、混合气成分设计（进气添加二氧化碳）、发动机参数调整（改变压缩比）等多种模式对二甲醚HCCI燃烧进行了研究和比较。试验结果表明,在不同工况下实时进行DME／LPG比例优化,通过改变燃料的理化特性和可燃混合气的成分,实现了HCCI着火与燃烧的有效控制,能够显著拓展二甲醚HCCI燃烧的运行负荷范围,并且各个工况下热效率最高、HC和CO排放最低。     

Cerium-promoted bi-functional hybrid materials made of Ni,Co and hydrotalcite for sorption-enhanced steam methane reforming (SESMR)

Multifunctional hybrid materials are promising for high-purity hydrogen (H₂) production via catalytic steam reforming coupled with low temperature on-site CO₂ capture. In the present work, novel hybrid materials made of Ni, Co (in varying proportions of 0–40%) and hydrotalcite (HTlc) were synthesized. The steam reforming activity of Ni was complemented by the high water-gas-shift (WGS) activity of Co. These unpromoted materials were referred to as Ni₁₀Co₃₀/HTlc (or HM1) and Ni₂₀Co₂₀/HTlc (or HM2). Thereafter, these materials were promoted with Ce species to improve the basicity and thermal stability of the composite material. The promoted materials were designated as Ce_2.5Ni₁₀Co₃₀/HTlc (or Ce-HM1) and Ce_2.5Ni₂₀Co₂₀/HTlc (or Ce-HM2). These materials were employed for sorption-enhanced steam methane reforming (or SESMR). The promotion with Ce resulted in strongly basic sites for CO₂ adsorption, and hence, improved H₂ production. Especially, Ce-HM1 exhibited the highest breakthrough time (45 min) and adsorption capacity (1.74 mol CO₂/kg sorbent), whereas Ce-HM2 exhibited a breakthrough time of 30 min and adsorption capacity of 1.51 mol CO₂/kg sorbent, producing >90 mol% H₂ at T = 773 K, P = 0.1 MPa, S/C = 6 mol/mol, and gas hourly space velocity or GHSV = 3600 mL/(g-h). High surface area and basicity of the promoted materials hindered coke formation and undesired reactions. Furthermore, with the improved catalytic activity and adsorption characteristics, these materials were stable and easily regenerable. When multi-cycle durability tests were performed for 25 cycles, it was found that both the promoted materials Ce-HM1 and Ce-HM2 remained stable for up to 21 and 16 cycles. Thus, promotion with Ce was valuable for producing pure H₂.     

Catalyst light-off behavior of a spark-ignition LPG (liquefied petroleum gas) engine during cold start

The effects of the length of the gas flow path from the exhaust outlet in the cylinder head to the catalyst inlet in the exhaust line, the ignition timing and the engine idle speed on the three-way catalyst light-off behavior in an electronically controlled inlet port LPG (liquefied petroleum gas) injection SI (spark-ignition) engine during cold start were investigated experimentally. The results showed that these factors affect the catalyst light-off behavior significantly during cold start. The reduction of the gas flow path length upstream the catalyst reduces the heat loss from the exhaust gases, increases the temperature of the catalyst, and results in faster catalyst light-off. Retarding the ignition timing from 0 to 15°CA ATDC decreases 22 and 8 s catalyst light-off time for HC and CO respectively. Increasing the engine idle speed from 1400 to 1800 rpm decreases 19 and 15 s the light-off time for HC and CO respectively.     

Thermodynamic analysis of steam reforming and oxidative steam reforming of propane and butane for hydrogen production

Thermodynamic analyses of cracking, partial oxidation (POX), steam reforming (SR) and oxidative steam reforming (OSR) of butane and propane (for comparison) were performed using the Gibbs free energy minimization method under the reaction conditions of T = 250–1000 °C, steam-to-carbon ratio (S/C) of 0.5–5 and O₂/HC (hydrocarbon) ratio of 0–2.4. The simulations for the cracking and POX processes showed that olefins and acetylene can be easily generated through the cracking reactions and can be removed by adding an appropriate amount of oxygen. For SR and OSR of propane and butane, predicted carbon formation only occurred at low S/C ratios (<2) with the maximum level of carbon formation at 550–650 °C. For the thermal-neutral conditions, the TN temperatures decrease with the increase of the S/C ratio (except for O/C = 0.6) and the decrease of the O/C ratio. The simulated results for SR or OSR of propane and butane are very close under the investigated conditions.     

A review on ethanol steam reforming for hydrogen production over Ni/Al2O3 and Ni/CeO2 based catalyst powders

Hydrogen is contemplated as an alternative clean fuel for the future. Ethanol steam reforming (ESR) is a carbon-neutral, sustainable, green hydrogen production method. Low cost Ni/Al₂O₃ and Ni/CeO₂ powder catalysts demonstrate high ESR activity. However, acidic nature of Al₂O₃ and instability of CeO₂ lead to deactivation of the catalysts easily. This article examines the research articles published on the modification of Ni by various noble and non-noble metals and on alteration of the supports by different metal oxides in detail and their effect on ESR all through 2000–2021. The ESR reaction mechanisms on Ni/Al₂O₃ and Ni/CeO₂ powder catalysts and basic thermodynamics for different possible reactions and H₂ yield are explored. Manipulation of catalyst morphology (surface area and particle size) via preparation method, selection of active metal promoter and support modifier are found to be significantly important for H₂ production and minimizing carbon deposition on catalysts.     

Pre-reforming of liquefied petroleum gas over nickel catalysts supported on magnesium aluminum mixed oxides

A series of Ni/Mg_xAl catalysts with different Mg/Al molar ratios were prepared by impregnating Mg-Al mixed oxides with nickel nitrate aqueous solution and used for the pre-reforming of LPG in the temperature range of 400-500 °C. XRD and H₂-TPR results showed that the Ni/Mg_xAl catalysts calcined at 800 °C mainly consisted of γ-Al₂O₃, Mg(Ni)Al₂O₄ and Mg(Ni)O phases varying with Mg/Al molar ratio without free NiO species observed. The effects of Mg/Al molar ratio, S/C molar ratio and reaction temperature on the catalytic behavior of the Ni/Mg_xAl catalysts were investigated in detail. The results revealed that the catalyst with Mg/Al molar ratio of 1.25 had the highest catalytic activity and stability. The increase in S/C molar ratio promoted both the steam reforming of LPG and the methanation of carbon oxides and hydrogen. The stability tests of 15%Ni/Mg_1.25Al catalyst showed that the catalyst was stable for the pre-reforming of LPG, and the stability decreased with elevating the reaction temperature due to more coke deposition.