Advanced Reaction Systems for Hydrogen Production

[EN] This PhD work started in March 2010 with the support of the University of the Basque Country (UPV/EHU) under the program named “Formación de Personal Investigador” at the Chemical and Environmental Engineering Department in the Faculty of Engineering of Bilbao. The major part of the Thesis work was carried out in the mentioned department, as a member of the Sustainable Process Engineering (SuPrEn) research group. In addition, this PhD Thesis includes the research work developed during a period of 6 months at the Institut für Mikrotechnik Mainz GmbH, IMM, in Germany. During the four years of the Thesis, conventional and microreactor systems were tested for several feedstocks renewable and non-renewable, gases and liquids through several reforming processes in order to produce hydrogen. For this purpose, new catalytic formulations which showed high activity, selectivity and stability were design. As a consequence, the PhD work performed allowed the publication of seven scientific articles in peer-reviewed journals. This PhD Thesis is divided into the following six chapters described below. The opportunity of this work is established on the basis of the transition period needed for moving from a petroleum based energy system to a renewable based new one. Consequently, the present global energy scenario was detailed in Chapter 1, and the role of hydrogen as a real alternative in the future energy system was justified based on several outlooks. Therefore, renewable and non-renewable hydrogen production routes were presented, explaining the corresponding benefits and drawbacks. Then, the raw materials used in this Thesis work were described and the most important issues regarding the processes and the characteristics of the catalytic formulations were explained. The introduction chapter finishes by introducing the concepts of decentralized production and process intensification with the use of microreactors. In addition, a small description of these innovative reaction systems and the benefits that entailed their use were also mentioned. In Chapter 2 the main objectives of this Thesis work are summarized. The development of advanced reaction systems for hydrogen rich mixtures production is the main objective. In addition, the use and comparison between two different reaction systems, (fixed bed reactor (FBR) and microreactor), the processing of renewable raw materials, the development of new, active, selective and stable catalytic formulations, and the optimization of the operating conditions were also established as additional partial objectives. Methane and natural gas (NG) steam reforming experimental results obtained when operated with microreactor and FBR systems are presented in Chapter 3. For these experiments nickel-based (Ni/Al2O3 and Ni/MgO) and noble metal-based (Pd/Al2O3 and Pt/Al2O3) catalysts were prepared by wet impregnation and their catalytic activity was measured at several temperatures, from 973 to 1073 K, different S/C ratios, from 1.0 to 2.0, and atmospheric pressure. The Weight Hourly Space Velocity (WHSV) was maintained constant in order to compare the catalytic activity in both reaction systems. The results obtained showed a better performance of the catalysts operating in microreactors. The Ni/MgO catalyst reached the highest hydrogen production yield at 1073 K and steam-to-carbon ratio (S/C) of 1.5 under Steam methane Reforming (SMR) conditions. In addition, this catalyst also showed good activity and stability under NG reforming at S/C=1.0 and 2.0. The Ni/Al2O3 catalyst also showed high activity and good stability and it was the catalyst reaching the highest methane conversion (72.9 %) and H2out/CH4in ratio (2.4) under SMR conditions at 1073 K and S/C=1.0. However, this catalyst suffered from deactivation when it was tested under NG reforming conditions. Regarding the activity measurements carried out with the noble metal-based catalysts in the microreactor systems, they suffered a very quick deactivation, probably because of the effects attributed to carbon deposition, which was detected by Scanning Electron Microscope (SEM). When the FBR was used no catalytic activity was measured with the catalysts under investigation, probably because they were operated at the same WHSV than the microreactors and these WHSVs were too high for FBR system. In Chapter 4 biogas reforming processes were studied. This chapter starts with an introduction explaining the properties of the biogas and the main production routes. Then, the experimental procedure carried out is detailed giving concrete information about the experimental set-up, defining the parameters measured, specifying the characteristics of the reactors used and describing the characterization techniques utilized. Each following section describes the results obtained from activity testing with the different catalysts prepared, which is subsequently summarized: Section 4.3: Biogas reforming processes using γ-Al2O3 based catalysts The activity results obtained by several Ni-based catalysts and a bimetallic Rh-Ni catalyst supported on magnesia or alumina modified with oxides like CeO2 and ZrO2 are presented in this section. In addition, an alumina-based commercial catalyst was tested in order to compare the activity results measured. Four different biogas reforming processes were studied using a FBR: dry reforming (DR), biogas steam reforming (BSR), biogas oxidative reforming (BOR) and tri-reforming (TR). For the BSR process different steam to carbon ratios (S/C) from 1.0 to 3.0, were tested. In the case of BOR process the oxygen-to-methane (O2/CH4) ratio was varied from 0.125 to 0.50. Finally, for TR processes different S/C ratios from 1.0 to 3.0, and O2/CH4 ratios of 0.25 and 0.50 were studied. Then, the catalysts which achieved high activity and stability were impregnated in a microreactor to explore the viability of process intensification. The operation with microreactors was carried out under the best experimental conditions measured in the FBR. In addition, the physicochemical characterization of the fresh and spent catalysts was carried out by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES), N2 physisorption, H2 chemisorption, Temperature Programmed Reduction (TPR), SEM, X-ray Photoelectron Spectroscopy (XPS) and X-ray powder Diffraction (XRD). Operating with the FBR, conversions close to the ones predicted by thermodynamic calculations were obtained by most of the catalysts tested. The Rh-Ni/Ce-Al2O3 catalyst obtained the highest hydrogen production yield in DR. In BSR process, the Ni/Ce-Al2O3 catalyst achieved the best activity results operating at S/C=1.0. In the case of BOR process, the Ni/Ce-Zr-Al2O3 catalyst showed the highest reactants conversion values operating at O2/CH4=0.25. Finally, in the TR process the Rh-Ni/Ce-Al2O3 catalyst obtained the best results operating at S/C=1.0 and O2/CH4=0.25. Therefore, these three catalysts were selected to be coated onto microchannels in order to test its performance under BOR and TR processes conditions. Although the operation using microreactors was carried out under considerably higher WHSV, similar conversions and yields as the ones measured in FBR were measured. Furthermore, attending to other measurements like Turnover Frequency (TOF) and Hydrogen Productivity (PROD), the values calculated for the catalysts tested in microreactors were one order of magnitude higher. Thus, due to the low dispersion degree measured by H2-chemisorption, the Ni/Ce-Al2O3 catalyst reached the highest TOF and PROD values. Section 4.4: Biogas reforming processes using Zeolites L based catalysts In this section three type of L zeolites, with different morphology and size, were synthesized and used as catalyst support. Then, for each type of L zeolite three nickel monometallic and their homologous Rh-Ni bimetallic catalysts were prepared by the wetness impregnation method. These catalysts were tested using the FBR under DR process and different conditions of BSR (S/C ratio of 1.0 and 2.0), BOR (O2/CH4 ratio of 0.25 and 0.50) and TR processes (at S/C=1.0 and O2/CH4=0.25). The characterization of these catalysts was also carried out by using the same techniques mentioned in the previous section. Very high methane and carbon dioxide conversion values were measured for almost all the catalysts under investigation. The experimental results evidenced the better catalytic behavior of the bimetallic catalysts as compared to the monometallic ones. Comparing the catalysts behavior with regards to their morphology, for the BSR process the Disc catalysts were the most active ones at the lowest S/C ratio tested. On the contrary, the Cylindrical (30–60 nm) catalysts were more active under BOR conditions at O2/CH4=0.25 and TR processes. By the contrary, the Cylindrical (1–3 µm) catalysts showed the worst activity results for both processes. Section 4.5: Biogas reforming processes using Na+ and Cs+ doped Zeolites LTL based catalysts A method for the synthesis of Linde Type L (LTL) zeolite under microwave-assisted hydrothermal conditions and its behavior as a support for heterogeneously catalyzed hydrogen production is described in this section. Then, rhodium and nickel-based bimetallic catalysts were prepared in order to be tested by DR process and BOR process at O2/CH4=0.25. Moreover, the characterization of the catalysts under investigation was also carried out. Higher activities were achieved by the catalysts prepared from the non-doped zeolites, Rh-Ni/D and Rh-Ni/N, as compared to the ones supported on Na+ and Cs+ exchanged supports. However, the differences between them were not very significant. In addition, the Na+ and Cs+ incorporation affected mainly to the Disc catalysts. Comparing the results obtained by these catalysts with the ones studied in the section 4.4, in general worst results were achieved under DR conditions and almost the same results when operated under BOR conditions. In Chapter 5 the ethylene glycol (EG) as feed for syngas production by steam reforming (SR) and oxidative steam reforming (OSR) was studied by using microchannel reactors. The product composition was determined at a S/C of 4.0, reaction temperatures between 625°C and 725°C, atmospheric pressure and Volume Hourly Space Velocities (VHSV) between 100 and 300 NL/(gcath). This work was divided in two sections. The first one corresponds to the introduction of the main and most promising EG production routes. Then, the new experimental procedure is detailed and the information about the experimental set-up and the measured parameters is described. The characterization was carried out using the same techniques as for the previous chapter. Then, the next sections correspond to the catalytic activity and catalysts characterization results. Section 5.3: xRh-cm and xRh-np catalysts for ethylene glycol reforming Initially, catalysts with different rhodium loading, from 1.0 to 5.0 wt. %, and supported on α-Al2O3 were prepared by two different preparation methods (conventional impregnation and separate nanoparticle synthesis). Then, the catalysts were compared regarding their measured activity and selectivity, as well as the characterization results obtained before and after the activity tests carried out. The samples prepared by a conventional impregnation method showed generally higher activity compared to catalysts prepared from Rh nanoparticles. By-product formation of species such as acetaldehyde, ethane and ethylene was detected, regardless if oxygen was added to the feed or not. Among the catalysts tested, the 2.5Rh-cm catalyst was considered the best one. Section 5.4: 2.5Rh-cm catalyst support modification with CeO2 and La2O3 In this part of the Chapter 5, the catalyst showing the best performance in the previous section, the 2.5Rh-Al2O3 catalyst, was selected in order to be improved. Therefore, new Rh based catalysts were designed using α-Al2O3 and being modified this support with different contents of CeO2 or La2O3 oxides. All the catalysts containing additives showed complete conversion and selectivities close to the equilibrium in both SR and OSR processes. In addition, for these catalysts the concentrations measured for the C2H4, CH4, CH3CHO and C2H6 by-products were very low. Finally, the 2.5Rh-20Ce catalyst was selected according to its catalytic activity and characterization results in order to run a stability test, which lasted more than 115 hours under stable operation. The last chapter, Chapter 6, summarizes the main conclusions achieved throughout this Thesis work. Although very high reactant conversions and rich hydrogen mixtures were obtained using a fixed bed reaction system, the use of microreactors improves the key issues, heat and mass transfer limitations, through which the reforming reactions are intensified. Therefore, they seem to be a very interesting and promising alternative for process intensification and decentralized production for remote application.

2-氨基-6-乙氧基苯并噻唑类偶氮染料及其金属鏊合物的合成及光学热学性能研究

合成了2-（2-氨基-6-乙氧基苯并噻唑基偶氮）-5-（N,N-二乙基氨基）三氟甲基磺酰苯胺偶氮染料（EBTDATFS）及其与乙酸镍、乙酸钴、乙酸铜、乙酸锌等金属盐鏊合的金属鏊合物。通过红外光谱、紫外-可见吸收光谱和MALDI质谱等对染料及其金属鏊合物进行了结构表征;使用旋涂方法在K9玻璃和抛光的单晶硅基片上制备薄膜;研究了镍金属鏊合物的热学性能;使用椭偏仪研究了Ni和Zn鏊合物的光学常数。结果表明：4种金属鏊合物薄膜最大吸收光谱为621-629nm,且长波边吸收峰陡峭;TGA-DSC测试结果表明镍金属鏊

Morphology observation of carbon deposition by CH4 decomposition over Ni-based catalysts

We found a novel morphology variation of carbon deposition derived from CH4 decomposition over NI-based catalysts. By altering the chemical composition and particle size of Ni-based catalysts, carbon filaments, nanofibres and nanotubes were observed over conventional Ni/y-Al2O3, Ni-Co/gamma-Al2O3 and nanoscale Ni-Co/gamma-Al2O3 catalysts, respectively. The simple introduction of Co into a conventional Ni/gamma-Al2O3 catalyst can vary the carbon deposition from amorphous filamentous carbon to ordered carbon fibres. Moreover, carbon nanotubes with uniform diameter distribution can be obtained over nanosized Ni-Co/gamma-Al2O3 catalyst particles. In addition, the oxidation behaviour of the different deposited carbon was studied by using a temperature-programmed oxidation technique. This work provides a simple strategy to control over the size and morphology of the carbon deposition from catalytic decomposition of CH4.

Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors

The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C6H3R2N=CH)(2)C6H3)LnCl(2)(THF)(2) (Ln = Y, R = Me (1), Et (2), Pr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C2H3-R2N=CH)(2)-C6H3Li and LnCl(3)(THF)(1 similar to 3.5). These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a kappa C:kappa N: kappa N' tridentate mode, adopting a meridional geometry.

Synthesis and characterization of phenylene-thiophene all-conjugated diblock copolymers

Grignard metathesis (GRIM) polymerization for all-conjugated diblock copolymers comprising poly (2,5-dihexyloxy-1,4-phenylene) (PPP) and poly(3-hexylthiophene) (P3HT) blocks were systematically studied with LiCl as additive and 1,2-bis (diphenylphosphino) ethane nickel dichloride (Ni(dppe)Cl-2) or 1,3-bis(diphenylphosphino) propane nickel dichloride (Ni(dppp)Cl-2) as catalyst. It was found that the addition order of the monomers was crucial for the success of copolymerization. With the monomer addition in the order of phenyl and then thienyl Grignard reagents, all-conjugated PPP-b-P3HT diblock copolymers with different block ratios were successfully synthesized. In contrast, the inverted addition order only afforded a mixture containing both block copolymers and deactivated or end-capped homopolymers.

Theoretical studies on the reaction mechanism of oxidation of primary alcohols by Zn/Cu(II)-phenoxyl radical catalyst

The catalytic mechanism for the oxidation of primary alcohols catalyzed by the two functional models of galactose oxidase (GOase), M-II L (M = Cu, Zn; L = N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)1-2-diiminoquinone)), has been studied by use of the density functional method B3LYP The catalytic cycle of Cu- and Zn-catalysts consists of two parts, namely, substrate oxidation (primary alcohol oxidation) and O-2 reduction (catalyst regeneration). The catalytic mechanisms have been studied for the two reaction pathways (route 1 and route 2). The calculations indicate that the hydrogen atom transfer within the substrate oxidation part is the rate-determining step for both catalysts, in agreement with the experimental observation.

Copolymerizations of ethylene with alpha-olefin-omega-ols by highly active vanadium(III) catalysts bearing [N,O] bidentate chelated ligands

The copolymerizations of ethylene with polar hydroxyl monomers such as 10-undecen-1-ol, 5-hexen-1-ol and 3-buten-1-ol were investigated by the vanadium(III) catalysts bearing bidentate [N,O] ligands (1, [PhN=C(CH3)CHC(Ph)O]VCl2(THF)(2): 2, [PhN=CHC6H4O]VCl2(THF)(2); 3, [PhN=CHC(Ph)CHO]VCl2(THF)(2)). The polar monomers were pretreated by alkylaluminum before the polymerization. High catalytic activities and efficient comonomer incorporations can be easily obtained by changing monomer masking reagents and polymerization conditions in the presence of diethylaluminium chloride as a cocatalyst. The longer the spacer group, the higher the incorporation of the monomer. Under the mild conditions, the incorporation level of 10-undecen-1-ol reached 13.9 mol% in the resultant copolymers was obtained. The reactivity ratios of copolymerization (r(1) = 41.4, r(2) = 0.02, r(1)r(2) = 0.83) were evaluated by Fineman-Ross method. According to C-13 NMR spectra, polar units were located both on the main chain and at the chain end.

Polypropylene as a carbon source for the synthesis of multi-walled carbon nanotubes via catalytic combustion

Multi-walled carbon nanotubes (MWCNTs) were efficiently synthesized by catalytic combustion of polypropylene (PP) using nickel compounds (such as Ni2O3, NiO, Ni(OH)(2) and NiCO3 (.) 2Ni(OH)(2)) as catalysts in the presence of organic-modified montmorillonite (OMMT) at 630-830 degrees C. Morphologies of the sample undergoing different combustion times were observed to investigate actual process producing MWCNTs by this method. The obtained MWCNTs were characterized by X-ray diffraction (XRD), transmission electron microscope and Raman spectroscopy. The yield of MWCNTs was affected by the composition of PP mixtures with OMMT and nickel compounds and the combustion temperature. The proton acidic sites from the degraded OMMT layers due to the Hoffman reaction of the modifiers at high temperature played an important role in the catalytic degradation of PP to supply carbon sources that are easy to be catalyzed by nickel catalyst for the growth of MWCNTs. The XRD measurements demonstrated that the nickel compounds were in situ reduced into the Ni(0) state with the aid of hydrogen gas and/or hydrocarbons in the degradation products of PP, and the Ni(O) was really the active site for the growth of MWCNTs. The combination of nickel compounds with OMMT was a key factor to efficiently synthesize MWCNTs via catalytic combustion of PP.

Effect of swelling response of the support particles on ethylene polymerization

Macroporous and modified macroporous poly(styrene-co-methyl methacrylate-co-divinylbenzene) particles (m-PS and mm-PS) supported Cp2ZrCl2 were prepared and applied to ethylene polymerization using methylaluminoxane (MAO) as cocatalyst. The influences of the swelling response of the support particles on the catalyst loading capabilities of the supports as well as on the activities of the supported catalysts were studied. It was shown that the Zr loadings of the supports and the activities of the supported catalysts increased with the swelling extent of the support particles. The m-PS or mm-PS supported catalysts exhibited very high activities when the support particles were well swollen, whereas those catalysts devoid of swelling treatment gave much lower activities. Investigation on the distribution of the supports in the polyethylene by TEM indicated that the swelling of the support particles allowed the fragmentation of the catalyst particles. In contrast, the fragmentation of the support particles with poor swelling was hindered during ethylene polymerization.

[Ni(OXPN) Ni(phen)_2 ](Cl O_4)_2 · 2H_2O的合成和性质

合成了新的双核配合物 [Ni(OXPN) Ni(phen) 2 ](Cl O4) 2 · 2 H2 O[OXPN=N,N′-双 - (3-氨丙基 )草酰胺 ],并进行了表征 .测定了对应单晶 [Ni(OXPN) Ni(phen) 2 ](Cl O4) 2 · 2 H2 O· CH3OH的结构及变温磁化率 (4～ 30 0 K) ,表明该配合物属 P1 空间群 ,a=0 .96 6 5 (4) nm,b=1.32 71(7) nm,c=1.716 3(5 ) nm,α=90 .42 (3)°,β=94.12 (3)°,γ=110 .6 4(4)°,V=2 .0 5 35 5 nm3.两个镍原子配位环境分别为平面四边形和畸变八面体构型 .以草酰二胺桥联的 Ni- Ni核间相距 0 .5 2 6 2 nm.磁化率测定表明两个镍原子间没有磁交换作用 ,说明一个镍原子处于平面四边形配位环境

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)(2) (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes (CpM)-M-#(NO)(SePh)(2) (M = Mo; Cp-# = Cp' (1a), MeCp (1b); M = W; Cp-# = Cp' (1c)) with (Norb)Mo(CO)(4), Ni(COD)(2) and Fe(CO)(5) have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)(4) in PhMe gave the bimetallic complexes: Cp'Mo(NO)(mu -SePh)(2)Mo(CO)(4) (2a), MeCpMo(NO)(mu -SePh)(2)Mo(CO)(4) (2b) and Cp'W(NO)(mu -SePh)(2)Mo(CO)(4) (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)(5) gave heterobimetallic complexes Cp'Mo(CO)(mu -SePh)(2)Fe(CO)(3) (3a) and Cp'W(NO)(mu -SePh)(2)Fe(CO)(3) (3c). Ni(COD)(2) reacts with two equivalents of (1a), (1b) and (1c) to give [Cp'Mo(NO)(mu -SePh)(2)](2)Ni (4a), [MeCpMo(NO)(mu -SePh)(2)](2)Ni (4b) and [Cp'W(NO)(mu -SePh)(2)](2)Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., H-1-n.m.r., C-13-n.m.r. and EI-MS spectroscopy.

Preparation and application of a novel core-shell-particle-supported zirconocene catalyst

The use of functional groups bearing silica/poly(styrene-co-4-vinylpyridine) core-shell particles as a support for a zirconocene catalyst in ethylene polymerization was studied. Several factors affecting the behavior of the supported catalyst and the properties of the resulting polymer, such as time, temperature, Al/N (molar ratio), and Al/Zr (molar ratio), were examined. The conditions of the supported catalyst preparation were more important than those of the ethylene polymerization. The state of the supported catalyst itself played a decisive role in both the catalytic behavior of the supported catalyst and the properties of polyethylene (PE). IR and X-ray photoelectron spectroscopy were used to follow the formation of the supports. The formation of cationic active species is hypothesized, and the performance of the core-shell-particle-supported zirconocene catalyst is discussed as well. The bulk density of the PE formed was higher than that of the polymer obtained from homogeneous and polymer-supported Cp2ZrCl2/methylaluminoxane catalyst systems. (C) 2001 John Wiley & Sons, Inc.

Preparation of poly(4-vinylpyridine)/silica hybrids supported cyclopentadienyltitanium trichloride (CpTiCl3) catalyst and styrene polymerization

Poly(4 - vinylpyridine)/silica( PVP/SiO2) organic - inorganic nanoscale hybrid was prepared using sol - gel method, in which PVP was used as an organic component and TEOS as a SiO2 precusor, This hybrid was used as CpTiCl3 support. The XPS and IR measurements showed that two kinds of catalytic active site were formed through analyzing the interaction mode between support and CpTiCl3. The results of styrene polymerization showed that syndiotactic was the highest at 50 degreesC. The catalytic activity was 1.09 x 10(6) g PS/ (mol Ti . h) at 70 degreesC when n(Al)/n(Ti) = 1500. GPC results showed a bimodal molecular weight distribution.

La_(2-x)Sr_xNiO_(4-λ)系列催化剂结构与氨氧化活性的关系

本文报道了La_(2-x)Sr_xNiO_(4-λ)(O≤x≤1)系列复合氧化物的固体结构性质和用于氨的氧化制硝酸的催化性能.La_(2-x)Sr_xNiO_(4-λ)的晶胞体积Ⅴ随x的增大而逐渐减小;c轴在x≤0.5前逐渐增大,在x≥0.5后逐渐减小.a轴在x≤0.5前逐渐减小,在x≥0.5后基本保持恒定.在x≤0.5前,La_(2-x)Sr_xNiO_(4-λ)中存在氧过剩,在x≥0.5后存在氧缺陷.TPD表明,a氧(吸附在氧缺陷上的氧)在x=0.6时出现极大,β氧(晶格氧)随x增大而逐渐增大.La_(2-x)Sr_xNiO_(4-λ)的氧化还原能力,Ni~(3+)的量,氨氧化的NO选择性都随x增大而增加.由此得出,Ni~(3+)是催化剂的活性离子,β氧是氨的氧化的活性氧种,在La_(2-x)Sr_xNiO_(4-λ)上的氨的氧化遵循氧化还原(Redox)机理.

峨眉山大火成岩省Ni-Cu-PGE矿床矿化类型变异机理研究

在峨眉山大火成岩省（ELIP）产出许多岩浆Cu-Ni-PGE岩浆硫化物矿床，如金宝山、杨柳坪、力马河、白马寨，以及大槽－阿布郎当矿化岩体。根据成矿元素组成特征，这些矿床可以区分为多种不同矿化类型，有以铂族元素为主贫铜镍的矿床，如金宝山Pt-Pd矿床；有含较高铂族元素和铜镍的矿床，如杨柳坪Ni-Cu-PGE矿床；也有贫铂族元素富铜镍的矿床，以力马河和白马寨Ni-Cu矿床最为典型。造成峨眉山大火成岩省中Ni-Cu-PGE岩浆硫化物矿床矿化类型变异的原因是什么？它们的母质岩浆性质如何，产生于怎样的熔融程度？既然能形成岩浆硫化物矿床，造成硫化物熔离的原因有哪些，什么因素起到了关键作用？这些矿化类型多样的Ni-Cu-PGE矿床的成矿岩浆有何差异？产生差异的原因是什么？带着这些疑问，通过借鉴国内外Ni-Cu-PGE岩浆硫化物矿床研究的经验，本文以金宝山铂钯矿、力马河镍矿及大槽－阿布郎当岩体的地球化学研究为基础，结合近几年来前人对杨柳坪，白马寨等矿床的系统研究，本文试图解决上述疑问。现在取得的主要认识有： 1） 根据成矿元素组成特征，可以把峨眉山大火成岩省中（ELIP）存在的Ni-Cu-PGE岩浆硫化物矿床分成多种不同的矿化类型，包括PGE矿床（例如金宝山Pt-Pd矿），Ni-Cu-PGE矿床（例如杨柳坪矿床），Ni-Cu矿床（例如力马河和白马寨矿床），以及弱矿化或不含矿的超镁铁质堆晶岩体（例如大槽－阿布郎当岩体）。通过对ELIP中几种类型Cu-Ni-PGE矿床成矿母岩浆的研究发现，它们均具有类似峨眉山苦橄岩的成分特征，表明母岩浆形成于较高程度的地幔部分熔融，并富集Ni和PGE。 2）硫化物熔离的多阶段性是导致矿床类型变异的一个重要因素。早期结晶矿物的分离结晶导致了金宝山母岩浆出现S的饱和，少量的浸染状硫化物被携带进入岩浆通道中发生了沉淀，继续富集PGE，形成了金宝山矿体。杨柳坪的母岩浆先发生了少量早期硫化物熔离丢失，PGE弱亏损的岩浆在后期上升过程中由于强烈的地壳混染，发生了大量硫化物熔离并发生堆积，形成杨柳坪矿体。力马河和白马寨的母岩浆在早期发生了较多的硫化物丢失，PGE强烈亏损的岩浆发生了二次以上的硫化物熔离，形成了力马河和白马寨矿体。 3） R因子（岩浆与熔离硫化物的比例）是决定ELIP中Cu-Ni-PGE矿床矿化类型变异的重要因素。金宝山矿床具有极高的R值（＞10000），杨柳坪和朱布矿床具有中等的R值（2000~5000），而力马河矿床近似为在经过R=2000的硫化物熔离之后，残余岩浆再经过R=200的硫化物熔离。 4） 地壳混染程度的差异可能是造成ELIP中Ni-Cu-PGE矿床矿化类型发生变异的关键因素。金宝山矿床的地壳混染程度较低，可能主要是早期橄榄石和铬铁矿的分异结晶导致了岩浆中硫化物出现了饱和。对于大槽－阿布郎当矿化岩体，只是在岩体边缘的局部出现了硫化物熔离，可能是围岩混染造成的。对于杨柳坪Ni-Cu-PGE矿床、力马河和白马寨Ni-Cu矿床，从微量元素蛛网中明显的Nb-Ta负异常，高放射成因187Os丰度的初始Os同位素组成（γOs(t)=100~120），S同位素等反映出显著的地壳混染，因而出现大量硫化物熔离。