Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

CO2合成醇酯类化学品和高分子材料研究进展

我国作为煤炭大国,燃烧化石燃料产生大量CO₂。通过化学作用将CO₂转化为能源燃料、基础化学品或高分子材料,有利于实现碳氧资源综合利用。从CO₂直接利用和间接利用的角度出发,分别综述了CO₂资源化利用研究进展。直接利用方面,重点阐述了CO₂直接加氢合成甲醇和乙醇;同时CO₂可作为羰化剂合成有机碳酸酯和高分子材料,包括碳酸二乙酯、聚碳酸酯和CO₂基可降解聚合物。在间接利用方面,重点综述了CO₂经碳酸乙烯酯的酯交换反应合成碳酸二甲酯,以及碳酸乙烯酯加氢制备甲醇联产乙二醇的研究进展。CO₂加氢直接合成甲醇催化剂主要包括铜基催化剂、贵金属催化剂,由于贵金属的成本高,廉价的Cu基催化剂研究较为广泛。CO₂加氢直接合成乙醇研究较广泛的催化剂为贵金属(Rh、Pd、Ru)基催化剂体系,还需进一步研究廉价、高活性和高稳定性的催化剂。CO₂与乙醇直接合成碳酸二乙酯(DEC)研究较多的催化剂为铈基多相催化剂,但由于生成物中水分的影响,限制了DEC的收率。环氧化物和CO₂耦合反应生成DEC过程中不产生水,可以有效克服热力学的限制,因此高能化合物与CO₂的耦合路线是高效制备DEC的有效途径。CO₂与环氧化物共聚制备聚碳酸酯材料多采用稀土三元催化剂体系,环氧化物的转化率和聚碳酸酯选择性较高,目前已经实现工业应用。CO₂通过碳酸乙烯酯与甲醇酯交换合成DMC,多使用碱性较强的催化剂和含碱性基团的离子交换树脂。CO₂经碳酸乙烯酯加氢制备甲醇和乙二醇的反应中,铜基催化剂展现出优异的催化性能。CO₂化学转化利用是CO₂碳氧资源综合利用的重要途径,将有效支撑我国未来碳中和目标实现。     

Hydrogenation of CO2 over sprayed Ru/TiO2 fine particles and strong metal–support interaction

Ru/TiO₂ catalysts were prepared by spray reaction (SPR) and conventional impregnation (IMP) methods. The catalytic activities of SPR fine particles were much higher than those of IMP catalysts for CO₂ hydrogenation. A high temperature reduction greatly promoted the activity of SPR catalyst. A model of surface structure was proposed which exhibits the enhancement of decoration and the formation of more boundaries over spr-Ru/TiO₂. The high activity of SPR catalyst is attributed to the occurrence of new active sites at the metal–support perimeters and not any SMSI phenomenon. EXAFS reveals that the Ru atom was interacting with TiO₂ by oxygen atom so strongly on the SPR catalysts that a part of the Ru atoms, located near the internal interface between Ru particles and TiO₂ support, existed as Ruⁿ⁺ (n<4) cations even if SPR catalyst was subjected to a high temperature reduction. These Ruⁿ⁺ cations are responsible for the inhibition of SMSI formation over SPR catalysts.     

Co/Al_2O_3催化剂制备及其合成重质烃的反应性能

以不同孔道结构Al_2O_3作载体,甲醇、乙醇和柠檬酸作分散剂,通过等体积浸渍法制备系列Co/Al_2O_3费托合成催化剂。采用XRD、TG-DSC和H2-TPR等考察制备方法对催化剂结构的影响,并在固定床反应器中对催化剂进行性能评价。结果表明,采用具有适宜孔道结构Al_2O_3作载体才能获得综合性能较好的催化剂,3种分散剂的加入,促进了钴物种在载体上的分散,增强了钴与载体间的相互作用,改善了催化剂费托合成反应活性,显著提高了重质烃时空收率。     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.     

Methanol synthesis from CO2-rich syngas over a ZrO2 doped CuZnO catalyst

ZrO₂-doped CuZnO catalyst prepared by successive-precipitation method was investigated by ICP-AES, BET, TEM, XRD, EXAFS, H₂-TPR and CO/CO₂ hydrogenation. The active phase of copper in CuZnO catalyst prepared by co-precipitation method was well-crystallized. The presence of ZrO₂ led to a high copper dispersion, which was distinctive from CuZnO. Though the activity for carbon monoxide hydrogenation was little lower than that of CuZnO catalyst, ZrO₂-doped CuZnO catalyst showed much higher activity and selectivity towards methanol synthesis from carbon dioxide hydrogenation. Moreover, ZrO₂-doped CuZnO catalyst showed high performance for methanol synthesis from CO₂-rich syngas.     

Coke study on MgO-promoted Ni/Al2O3 catalyst in combined H2O and CO2 reforming of methane for gas to liquid (GTL) process

MgO-promoted Ni/Al₂O₃ catalysts have been investigated with respect to catalytic activity and coke formation in combined steam and carbon dioxide reforming of methane (CSCRM) to develop a highly active and stable catalyst for gas to liquid (GTL) processes. Ni/Al₂O₃ catalysts were promoted through varying the MgO content by the incipient wetness method. X-ray diffraction (XRD), BET surface area, H₂-temperature programmed reduction (TPR), H₂-chemisorption and CO₂-temperature programmed desorption (TPD) were used to observe the characteristics of the prepared catalysts. The coke formation and amount in used catalysts were examined by SEM and TGA, respectively. H₂/CO ratio of 2 was achieved in CSCRM by controlling the feed H₂O/CO₂ ratio. The catalysts prepared with 20 wt.% MgO exhibit the highest catalytic performance and have high coke resistance in CSCRM. MgO promotion forms MgAl₂O₄ spinel phase, which is stable at high temperatures and effectively prevents coke formation by increasing the CO₂ adsorption due to the increase in base strength on the surface of catalyst.     

Hydrogenation of carbon dioxide to methanol over palladium-promoted Cu/ZnO/A12O3 catalysts

The effect of Pd on a Cu/ZnO/A1₂O₃ catalyst for methanol synthesis from CO₂/H₂ has been investigated. Activities of impregnated catalysts and physical mixtures were studied in an internal recycle reactor under 5 MPa, 250°C and a range of conversions. In all cases, the promotion of methanol production was greater at higher flow rates (lower conversions). The promotion achieved by use of Pd/A1₂O₃+ Cu/ZnO/Al₂O₃ physical mixtures was found to increase with Pd content. Greater promotion was observed over the Pd impregnated Cu/ZnO/Al₂O₃ catalysts, although this was insensitive to the particular Pd loadings used. The results are consistent with the proposal that hydrogen spillover is responsible for the observed promotion. The effectiveness of Pd as a promoter for the reduction of CuO in the catalysts was studied by TPR and was found to be related to the level of promotion in methanol production.     

CO_2催化加氢制甲醇进展

CO_2的大量排放给人类生存环境带来威胁的同时也造成资源的严重浪费,实现资源→CO_2→资源的可持续循环是解决该问题的理想途径,因此,CO_2加氢制甲醇倍受关注。国外完成中试试验,国内仍处于小试阶段。受CO_2富集及H_2制取成本的限制,CO_2加氢制甲醇技术须利用先进技术与可再生资源获得廉价的原料气。Cu-Zn系催化剂为有工业化前景的CO_2加氢制甲醇催化剂,但存在活性与选择性差的问题,未来活性组分高度分散和具有高比表面积的纳米催化材料的研制是比较可行的研究思路。     

Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2

Among various Cu/ZnO/ZrO₂ catalysts with the Cu/Zn ratio of 3/7, the one with 15 wt.% of ZrO₂ obtains the best activity for methanol synthesis by hydrogenation of CO. The TPR, TPO and XPS analyses reveal that a new copper oxide phase is formed in the calcined Cu/ZnO/ZrO₂ catalysts by the dissolution of zirconium ions in copper oxide. In addition, the Cu/ZnO/ZrO₂ catalyst with 15 wt.% of ZrO₂ turns out to contain the largest amount of the new copper oxide phase. When the Cu/ZnO/ZrO₂ catalysts is reduced, the Cu²⁺ species present in the ZrO₂ lattice is transformed to Cu⁺ species. This leads to the speculation that the addition of ZrO₂ to Cu/ZnO catalysts gives rise to the formation of Cu⁺ species, which is related to the methanol synthesis activity of Cu/ZnO/ZrO₂ catalyst in addition to Cu metal particles. Consequently, the ratio of Cu⁺/Cu⁰ is an important factor for the specific activity of Cu/ZnO/ZrO₂ catalyst for methanol synthesis.     

Methanol synthesis from CO2 over Cu/ZnO catalysts prepared from various coprecipitated precursors

Various precursors of Cu/ZnO catalysts were prepared by coprecipitation methods. By varying the conditions of coprecipitation, precursors having different structures (aurichalcite, malachite, hydrozincite, or their mixture) were obtained at given Cu/Zn ratios, ranging from 30/70 to 70/30. In a wide range of the Cu/Zn ratios, the catalysts derived from the precursors containing aurichalcite exhibited high performance in the methanol synthesis from CO₂.     

Comparative study of synthesis of methylamines from carbon oxides and ammonia over Cu/A12O3

Methylamines have been synthesized from carbon dioxide, hydrogen and ammonia using Cu/Al₂O₃ catalysts with different copper loading. The reaction was performed in a fixed-bed micro reactor in the temperature range 473–573 K and at 0.6 MPa total pressure. The product amines were mono-, di- and trimethylamine (MMA, DMA, TMA). The distribution of the amines depended mainly on the reaction temperature and the NH₃/CO₂ ratio in the feed gas. At elevated temperatures and higher NH₃ concentrations methanol synthesis is suppressed and MMA is the main amine product, reaching a ratio of MMA:DMA:TMA of 1:0.23:0.07. Conversion and product distribution were compared to that of the corresponding reaction starting from CO or methanol instead of CO₂. With CO conversion was lower but the selectivity to MMA was higher. If CO₂ was replaced by methanol, conversion increased and TMA was the main product. In all experiments a change of space velocity had relatively little influence on both conversion and distribution of amines.     

Development of high performance Raney Cu-based catalysts for methanol synthesis from CO2 and H2

Catalytic hydrogenation of CO₂ into methanol has been investigated over Raney Cu-based catalysts. The Raney catalysts leached in NaOH/ZnO solutions showed high activities and selectivities for methanol synthesis. The deposition of Zn on the surface of Cu particles increased the surface area and the specific activity of Raney Cu–M. Raney Cu–Zr developed was significantly more active than a commercial catalyst.     

Characterization and catalytic activity of soft-templated NiO-CeO2 mixed oxides for CO and CO2 co-methanation

Nanosized NiO,CeO₂ and NiO-CeO₂ mixed oxides with different Ni/Ce molar ratios were prepared by the soft template method.All the samples were characterized by different techniques as to their chemical composition,structure,morphology and texture.On the catalysts submitted to the same reduction pretreatment adopted for the activity tests the surface basic properties and specific metal surface area were also determined.NiO and CeO₂ nanocrystals of about 4 nm in size were obtained,regardless of the Ni/Ce molar ratio.The Raman and X-ray photoelectron spectroscopy results proved the formation of defective sites at the NiO-CeO₂ interface,where Ni species are in strong interaction with the support.The microcalorimetric and Fourier transform infrared analyses of the reduced samples highlighted that,unlike metallic nickel,CeO₂ is able to effectively adsorb CO₂,forming carbonates and hydrogen carbonates.After reduction in H2 at 400°C for 1 h,the catalytic performance was studied in the CO and CO₂ co-methanation reaction.Catalytic tests were performed at atmospheric pressure and 300°C,using CO/CO₂/H₂ molar compositions of 1/1/7 or 1/1/5,and space velocities equal to 72000 or 450000 cm³?h^-1?gcat^-1.Whereas CO was almost completely hydrogenated in any investigated experimental conditions,CO₂ conversion was strongly affected by both the CO/CO₂/H₂ ratio and the space velocity.The faster and definitely preferred CO hydrogenation was explained in the light of the different mechanisms of CO and CO₂ methanation.On a selected sample,the influence of the reaction temperature and of a higher number of space velocity values,as well as the stability,were also studied.Provided that the Ni content is optimized,the NiCe system investigated was very promising,being highly active for the CO_x co-methanation reaction in a wide range of operating conditions and stable(up to 50 h)also when submitted to thermal stress.     

CO_2制备甲醇催化剂研究进展

通过将CO2有效转化为甲醇,真正实现"跨越油气时代"进入"甲醇时代"。通常CO2加氢合成甲醇所用催化剂主要是铜基催化剂,添加其他金属元素或助剂以提高铜基催化剂催化性能。介绍CO2制备甲醇催化剂早期的研究,综述近年来有关CO2制备甲醇催化剂研究进展,新研发的镍-镓结构催化剂可在低压(常压)下将CO2转化为甲醇,比传统的铜-锌-铝催化剂更有效,更多产甲醇。介绍CO2与水反应合成甲醇反应所用催化剂以及光催化还原CO2生成甲醇的新思路和新途径。     

Hydrocarbon synthesis through CO2 hydrogenation over CuZnOZrO2/zeolite hybrid catalysts

Direct syntheses of hydrocarbons from CO₂ hydrogenation were investigated over hybrid catalysts consisting of methanol synthesis catalyst (CuZnOZrO₂) and zeolites (MFI and SAPO). The yield of hydrocarbons was strongly depending upon the amount of zeolite's acid sites as measured by NH₃ TPD, while the product distributions were hardly affected by the change of acidity. The main product was ethane in the case of MFI hybrid catalyst and C₃ or C₄ hydrocarbon in the case of SAPO hybrid catalyst. This difference in product distribution was attributed to different mechanism of hydrocarbon formation. Investigation based on the ethene co-reaction suggested that the consecutive mechanism operated for HZSM-5 and the carbon pool mechanism for SAPO.     

Cu/ZnO/Zn-Al水滑石催化剂的制备及在富CO_2合成气制甲醇反应中的催化性能

传统Cu/ZnO/Al_2O_3(CZA)甲醇合成催化剂在富CO_2合成气制甲醇反应中的性能不高。为了提高CZA催化剂的性能,采用并流沉淀-水热老化法制备Zn-Al水滑石(Zn-Al-HT)载体,与Cu-Zn母体复合得到Cu-ZnO/Zn-Al-HT(HCZA)催化剂。对载体以及催化剂进行表征,考察不同水滑石含量的HCZAx(x=1~4)催化剂在富CO_2合成气制甲醇反应中的催化性能,并在HCZA3催化剂上进行120h稳定性试验。结果表明,还原态催化剂上Cu比表面积越大,催化剂上总碳转化率越高;催化剂中Zn-Al-HT相含量越高,液相有机相中甲醇含量越高;HCZA3催化剂具有良好的催化稳定性。     

甲醇和乙醇合成异丁醛La-V/TiO_2-SiO_2催化剂的制备及其催化性能

以V_2O_5为活性组分,通过对催化剂活性组分、载体结构和助剂等因素的研究,制备La-V/TiO_2-SiO_2催化剂,在n(甲醇)∶n(乙醇)=4∶1、空速1.5 h-1、氮气流量120 m L·min~(-1)、反应温度360℃和常压条件下,乙醇转化率84%,异丁醛选择性67%。     

Catalytic performance for CO2 conversion to methanol of gallium-promoted copper-based catalysts: influence of metallic precursors

This study reports new gallium-promoted copper-based catalysts prepared by co-impregnation of methoxide–acetylacetonate (acac) precursors from methanolic solutions onto silica and zinc oxide supports. Catalyst performance in the CO₂ hydrogenation to methanol was investigated at 2 MPa and temperatures between 523 and 543 K. A high activity and selectivity for ZnO-supported catalysts was found, which also showed a high stability in terms of both activity and selectivity. The maximum value for the activity was 378 g MeOH/kg cat h at 543 K, with a selectivity of 88% towards methanol production. The high performance of these materials in the CO₂ hydrogenation is related to the presence of Ga₂O₃ promoter and highly dispersed Cu⁺ species on the surface, determined by XPS and Auger on used catalysts.