高温环境下催化裂化催化剂磨损状况的研究

为研究流化催化裂化(FCC)催化剂在高温环境下的磨损行为,在一套固定流化床装置中考察了FCC平衡剂CGP-I在500℃和600℃高温环境下磨损率的时变关系和过孔气速对磨损率的影响,分别从颗粒形貌、磨损动力学等方面对催化剂的磨损机制进行了研究。结果表明:随着磨损时间的延长,磨损速率逐渐下降;随着磨损温度和孔气速的增加,磨损率增大。通过分析结果并与Gwyn磨损动力学方程比较建立了宏观磨损平衡方程,整个磨损过程可近似看作一级不可逆过程,该催化剂磨损率随磨损时间和孔气速的升高呈指数关系增加,高温环境下催化剂的磨损行为主要受表层磨损机制支配。     

Development of new nickel based catalyst for tar reforming with superior resistance to sulfur poisoning and coking in biomass gasification

Gasification of tar by catalytic steam reforming was examined in the gasification process of biomass, such as dried sewage sludge and wood chips. The tar reforming characteristics of the newly-developed Ni/MgO–CaO (based on dolomite) catalyst which was doped with WO₃ as a sulfur-resistant promoter, was investigated using a simulated gas containing naphthalene as tar. The result has confirmed that the developed catalyst shows a high naphthalene reforming activity and is stable even in gas containing hydrogen sulfide. The catalyst also exhibited superior resistance to coking as well as sulfur poisoning compared to several commercial steam-reforming catalysts.     

Application of engineered natural ores to intermediate- and high-temperature CO2 capture and conversion

Integrated CO₂ capture and conversion (ICCC) is a promising technology aiming at converting waste CO₂ to fuels and high value-added chemicals. Herein, we described a proof-of-concept study of applying engineered natural ores (dolomite, magnesite, and limestone) to two different ICCC processes—intermediate-temperature ICCC for CH₄ production (350–400°C) and high-temperature ICCC for syngas production (650–700°C). In the former process, a MgO-based CO₂ sorbent prepared from dolomite and magnesite was combined with a methanation catalyst in a dual-bed configuration, whereby a CH₄ yield of 7.1–7.3 mmol/g can be stably achieved per cycle over 20 consecutive ICCC cycles. In the latter process, a CaO-based sorbent derived from dolomite and limestone was coupled with a reforming catalyst also in a dual-bed mode, whereby syngas with a H₂/CO ratio of 0.9–1.0 can be produced over 20 cycles. This study will expand the application of natural ores in CO₂ emission reduction.     

Synthetic Ca‐based solid sorbents suitable for capturing CO2 in a fluidized bed

Coprecipitation and hydrolysis of CaO have been employed to produce Ca‐based synthetic sorbents suitable for capturing CO₂ in a fluidized bed. Their composition, CO₂ uptake, volume in small pores (2–200 nm) and resistance to attrition were measured and compared to those of limestone and dolomite. Sorbents produced by hydrolysis showed the highest uptake and resistance to attrition. After 20 cycles of carbonation and calcination, two sorbents exceeded the uptake of both limestone and dolomite, when subjected to the same regimes of reaction. A sorbent's uptake of CO₂ was shown to be determined by the volume in pores narrower than ～200 nm.     

流化床甲醇合成催化剂的制备及其性能

采用碳酸钠共沉淀法制备了5种不同组成的铜基甲醇合成催化剂,并对其进行了活性评价和形貌及抗磨损性能表征. 结果表明,氧化锆可使催化剂的耐磨损强度显著提高,磨损指数(AJI)可达0.056;催化剂的活性和稳定性较好,CO转化率约40%,260℃高温下长达50 h基本不失活. 氧化铝与铜锌发生复合使催化剂的活性显著下降,CO转化率仅有10%,对催化剂的强度提高作用不明显,AJI值达0.103. 组成为铜锌锆的催化剂较适用于流化床中甲醇的合成.     

Jet cup attrition testing

Jet cup attrition testing is a common method for evaluating particle attrition in fixed fluidized beds and circulating fluidized beds. An attrition index, calculated from jet cup data, is used to compare with one or more reference materials. However, this method is far from perfect despite its popularity. Results obtained at Particulate Solid Research, Inc. (PSRI) in different-sized jet cups and a 29-cm (11.5-in.) diameter fluidized bed test unit did not provide the same ranking of catalyst with respect to particle attrition. To obtain a better understanding of attrition in a jet cup, both computational fluid dynamics (CFD) and cold flow studies were performed with a 2.5-cm (1-in.) diameter Davison-type jet cup and PSRI's cylindrical 7.6-cm (3-in.) diameter jet cup. Results showed that a significant amount of material in the Davison and PSRI jet cup remained stagnant. Based on these results and additional CFD modeling, PSRI designed a new jet cup, where most of the material was hydrodynamically active. The new jet cup showed a 25% increase in attrition compared to PSRI's cylindrical jet cup under similar conditions and run times. Results were also compared to cyclone attrition data for several materials at PSRI. The new jet cup provided data that correlated with attrition results from the 29-cm (11.5-in.) diameter fluidized bed unit.     

Sorption enhanced steam methane reforming by Ni/CaO/mayenite combined systems: Overview of experimental results from European research project ASCENT

Work Package 4 (WP4) of the European research project ASCENT developed combined sorbent-catalyst materials (CSCM) for sorption enhanced steam methane reforming (SESMR), based on nickel (Ni) and calcium oxide (CaO). This work summarizes the whole experimental study carried out in ASCENT WP4 on Ni/CaO/mayenite systems obtained from wet mixing and wet impregnation synthesis methods. Effects from Ni precursor (Ni (CH₃COO)₂ · 4H₂O or Ni(NO₃)₂ · 6H₂O), Ni load (from 3 wt%-10 wt%), and free CaO load (from 0 wt%-54 wt%) were investigated for 26 materials by means of characterizations and reforming reactivity tests in a packed-bed microreactor (650°C, 1 atm). Thanks to comparative analyses of the results, evidence emerged about the detrimental influence of low Ni/CaO ratio on the reforming catalytic activity of solid inventories, made of CSCM or even of the raw mixing of CaO-mayenite and Ni-mayenite particles. Catalytic materials were active towards reforming only when derived from Ni(NO₃)₂ · 6H₂O. Based on this, the best CSCM (with the lowest free CaO content and the highest Ni load from nickel nitrate) was chosen to further study its industrial applicability by multicycle SESMR/sorbent-regeneration tests in a bench-scale packed-bed rig and attrition tests according to ASTM D5757-11. The CSCM was stable and active for 200 cycles with regenerations in N₂ at 850°C, while a progressive loss of its activity occurred with regenerations in CO₂ at 925°C as the cycle number increased due to Ni sintering. Its performance in the attrition tests was comparable to that of calcined dolomite.     

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.     

Estimation of concentration and temperature profiles for methane-steam reforming reaction in a porous catalyst

This work represents the results of the theoretical study of the distribution of concentration and temperature in porous catalyst, carried out over spherical catalyst pellets for the methane-steam reforming reaction over Ni/MgAl₂O₄ catalyst. Kinetic information has been taken from a recent study [J. Xu, F.G. Froment, AIChE J. (35) (1989) 88–96] for the above reaction. The mass and heat transfer distribution coupled with chemical reaction, outside and within the catalyst particles for methane-steam reforming reaction was estimated in this present study. A computer program was written to calculate both concentration profile and temperature profile for the methane-steam reforming reaction.     

Factors affecting methanol photocatalytic oxidation and catalyst attrition in a fluidized-bed reactor

A resolution IV fractional factorial experimental design explored the effects of seven factors on both the methanol photocatalytic oxidation (PCO) rate and the catalyst particle size distribution using a fluidized-bed reactor. The seven factors were as follows: calcination temperature, calcination time, grinding order, particle size, vibration amplitude, carrier gas humidity, and fluidization velocity. Decreasing calcination temperature from 726 to 623 K increased the activity of TiO₂/Al₂O₃ catalysts for methanol PCO. Attrition during fluidization liberated small TiO₂ particles from the bulk catalyst and the rate of attrition increased with gas velocity. Attrition was the primary cause of catalyst elutriation and not the presence of fine particles initially present in the bed from catalyst preparation. Increasing humidity caused agglomeration of fine particles, which reduced the amount of catalyst carryover. Removal of fines from the catalyst bed prior to fluidization caused an increase in catalyst attrition until the amount of fines present in the bed was similar to that of a bed in which fines were not removed.     

Hydrogen Production by Steam Reforming of Liquefied Natural Gas Over Mesoporous Ni-Al2O3 Composite Catalyst Prepared by a Single-step Non-ionic Surfactant-templating Method

A mesoporous Ni-Al₂O₃ composite catalyst (Ni-A-NS) was prepared by a single-step non-ionic surfactant-templating method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on mesoporous alumina (Ni/A-NS) was also prepared by an impregnation method. The effect of physicochemical properties on the performance of Ni-A-NS catalyst in the steam reforming of LNG was investigated. Ni-A-NS catalyst retained superior textural properties compared to Ni/A-NS catalyst. Nickel oxide species were highly dispersed on the surface of both Ni/A-NS and Ni-A-NS catalysts through the formation of surface nickel aluminate phase. Although both Ni/A-NS and Ni-A-NS catalysts exhibited a stable catalytic performance, Ni-A-NS catalyst showed a better catalytic performance than Ni/A-NS catalyst in the steam reforming of LNG. High nickel surface area and high nickel dispersion of Ni-A-NS catalyst played an important role in enhancing the dehydrogenation reaction of hydrocarbon species and the gasification reaction of adsorbed carbon species in the steam reforming of LNG. High reducibility of Ni-A-NS catalyst was also responsible for its high catalytic performance.     

Attrition behavior of fine particles in a fluidized bed with bimodal particles: Influence of particle density and size ratio

To process the solid particulates in fluidized bed and slurry phase reactors, attrition is an inevitable consequence and is therefore one of the preliminary parameters for the catalyst design. In this paper, the mechanical degradation propensity of the zeolite catalysts (particles) was investigated in a bimodal distribution environment using a Gas Jet Attrition — ASTM standard fluidized bed test (D-5757). The experimentation was conducted in order to explore parameters affecting attrition phenomena in a bimodal fluidization. In a bimodal fluidization system, two different types of particles are co-fluidized isothermally. The air jet attrition index (AJI) showed distinct increases in the attrition rate of small particles in a bimodal fluidization environment under standard operating conditions, in comparison with single particle. A series of experiments were conducted using particles of various sizes, with large particles of different densities and sizes. Experimental results suggest that the relative density and particle size ratio have a significant influence on attrition behavior during co-fluidization. Therefore a generalized relationship has been drawn using Gwyn constants; those defined material properties of small particles. Moreover, distinct attrition incremental phenomenon was observed during co-fluidization owing to the change in collision pattern and impact, which was associated with relative particle density and size ratios.     

CO2 reforming of CH4 in coke oven gas to syngas over coal char catalyst

The CO₂ reforming of methane (in coke oven gas) on the coal char catalyst was performed in a fixed bed reactor at temperatures between 800 and 1200 °C under normal pressure. The effects of the coal char catalyst pretreatment and the ratio of CO₂/CH₄ were studied. Experimental results showed that the coal char was an effective catalyst for production of syngas, and addition of CO₂ did not enhance the CH₄ reforming to H₂. It was also found that the product gas ratio of H₂/CO is strongly influenced by the feed ratio of CO₂/CH₄. The modified coal char catalyst was more active during the CO₂–CH₄ reforming than the coal char catalyst based on the catalyst volume, furthermore the modified catalyst exhibited high activity in CO₂–CH₄ reforming to syngas. The conversion of methane can be divided into two stages. In the first stage, the conversion of CH₄ gradually decreased. In the second stage, the conversion of methane maintained nearly constant. The conversion of CO₂ decreased slightly during the overall reactions in CO₂–CH₄ reforming. The coal char catalyst is a highly promising catalyst for the CO₂ reforming of methane to syngas.     

Reforming of Methane with Carbon Dioxide over a Catalyst Consisting of Ruthenium Metal and Cerium Oxide Supported on Mordenite

Reforming of CH₄ with CO₂ proceeds at 400 °C over a catalyst consisting of ruthenium metal and CeO₂ highly dispersed on mordenite. The catalyst, Ru-CeO₂/MZ, is highly active for the reforming of CH₄ under the conditions at which a carbon formation reaction is thermodynamically apt to take place. The reforming selectively forms H₂ and CO. An increase in the weight of the catalyst resulting from carbon deposits was scarcely observed. IR spectra for the catalyst indicate that the reforming proceeds via the formation of the intermediate species such as Ru-CO and Ru-CH_x on the surface of ruthenium. The data of H₂ adsorption support the idea that ruthenium is highly dispersed in Ru-CeO₂/MZ.     

Catalytic reforming of tar during gasification. Part I. Steam reforming of biomass tar using ilmenite as a catalyst

Ilmenite, a natural iron-containing mineral, has been investigated as an inexpensive catalyst for the steam reforming of volatiles (tar) from the pyrolysis of mallee woody biomass. The results indicate that ilmenite has good activity for the steam reforming of tar into gases due to its highly dispersed iron-containing species. The supply of external steam, in addition to the H₂O and CO₂ produced during the pyrolysis of biomass, plays an important role in minimising the formation of coke on the catalyst surface and thus the catalyst activity. The catalyst deactivation due to coke formation has more adverse effects on the reforming of larger aromatic ring system with steam than that of smaller ones. In addition, the supply of additional oxygen at low concentration changed the outcomes of tar reforming mainly because oxygen activated the smaller aromatic ring systems and polymerised them into larger aromatic ring systems in the gas phase.     

Coke deposition mechanism on the pores of a commercial Pt-Re/γ-Al2O3 naphtha reforming catalyst

Coke deposition mechanism on a commercial Pt-Re/γ-Al₂O₃ naphtha reforming catalyst was studied. A used catalyst that was in industrial reforming operation for 28 months, as well as the fresh catalyst of the unit were characterized using XRD, XRF, and nitrogen adsorption/desorption analyses. Carbon and sulfur contents of the fresh and the used catalysts were determined using Leco combustion analyzer. The pore size distributions (PSD) of the fresh and the used reforming catalysts were determined using BJH and Comparison Plot methods. The Comparison Plot method produced the most reasonable PSDs for the catalysts. Through comparison of the PSDs of the fresh and the used catalysts, it was revealed that coke deposited on both micropores and mesopores of the catalyst at a constant thickness of 1.0 nm. The constant coke thickness on the catalyst pore walls in the naphtha reforming process (temp. ∼ 500 °C) implies that coke deposition reaction is the slow controlling step in comparison to the fast mass transfer rate of coke ingredients into the pores. The bulk density of the deposited coke on the used catalyst was calculated as 0.966 g/cm³.     

Hydrogen production from fluidized bed steam reforming of hydrocarbons

Steam reforming of methane, kerosene and heavy oil over a nickel/alumina commercial catalyst and other materials such as limestone, dolomite and iron ore, was studied using a 5 cm i.d. fluidized bed reactor. The effects of operating parameters on conversion, hydrogen yield, product gas composition and elutriation of fine catalysts were investigated. It was found that a fluidized bed is flexible enough to handle various feedstocks, including hydrocarbons heavier than naphtha, because it permits the addition of catalyst to, or withdrawals of, coked catalyst from the bed. The yield of hydrogen obtained from fluidized bed steam reforming of heavy oil at 800‡C over limestone was similar to that obtained over commercial nickel-based catalyst. This indicates that limestone could be a promising catalyst for the production of hydrogen from heavy oil. However, hydrogen yield decreased with reaction time in the experiments using the limestone catalyst. The main cause of the decrease in hydrogen yield was elutriation of fine catalysts from the bed during the reaction.     

Comparison of mechanical strength of reforming catalysts of different geometry

Manufacturing of the first commercial lot of sphere-shaped reforming catalyst granules for units with a fixed catalyst bed and relevance of wide-scale application of sphere-shaped catalysts instead of extrudates made it necessary to compare mechanical crushing and attrition strengths of reforming catalysts having the form of cylinder-shaped extrudates and spherical granules. No such data have been published as of yet. The advantages of spherical catalysts for semi-regenerative reforming units, which is attributed to the absence of fines, the ability to form a dense bed, as well as practical convenience for the end users working with spherical catalysts are show. The results of the operation of the first test lot of RB-44U “Sh” spherical catalyst at a commercial unit which confirm high strength parameters and point to increased activity and selectivity are demonstrated. The presented collection of the data reveals advantages of sphere-shaped catalysts, namely their mechanical strength and some properties associated with catalyst utilization.     

生物质催化气化实验研究

在常压流化床上进行了生物质在水蒸气条件下的实验研究。实验装置主体由常压流化床反应器和固定床催化裂解反应器组合而成。生物质原料为木屑,焦油裂解催化剂分别选用煅烧白云石和镍基重整催化剂。实验结果表明,H2/CO(H/C)的摩尔比随着气化温度、水蒸气质量/生物质质量（S/B）的升高迅速增加,但催化裂解温度变化对H/C的影响较小。另外,在催化裂解反应器中使用催化剂种类不同,H/C也不同。本文采用两段催化裂解,一段催化剂采用煅烧白云石,二段采用镍基催化剂,焦油裂解率达到96.70％。采用两段催化裂解,不但可以提高焦油的裂解率,增加了H2和CO收率,净化生物质裂解气,而且可以防止镍基重整催化剂失活,延长其使用寿命。     

Stabilization of bio-oil over a low cost dolomite catalyst

A low cost alkaline catalyst of dolomite (CaMg(CO₃)₂) was used to stabilize acacia sawdust bio-oil mixed with methanol. The upgrading efficiency was evaluated in terms of the total acid number (TAN) and viscosity. A change in the dolomite calcination temperature from 700 to 900 °C led to a significant change in the TAN and viscosity of the methanol-added bio-oil. Dolomite activated at higher temperatures had larger amounts of active CaO and MgO species due to the enhanced decarboxylation of calcium and magnesium carbonates. An increase in the dolomite content (1-5 wt%) decreased the TAN value of bio-oil remarkably. A thermal aging test of the methanol-added bio-oil upgraded using dolomite (calcined at 900 °C) at 50 °C for 24 h was carried out by storing the bio-oil at 80 °C for one week. Although the TAN value increased after the aging process, it was still lower than the TAN of raw bio-oil. In addition, increasing the methanol content (10-30 wt%) decreased the TAN and viscosity of the bio-oil significantly.