The use of various metal carbonyls as catalyst precursors for coal hydroliquefaction

The catalytic activity of metal carbonyl complexes of chromium, molybdenum, tungsten, manganese, iron, cobalt, and nickel in the liquefaction of coal (Illinois No. 6, Wandoan and Mi-ike) was investigated. The carbonyl compounds of molybdenum, tungsten, iron, cobalt, and nickel acted as highly active catalysts for the liquefaction of Illinois No. 6 coal, resulting in high coal conversion (>90%) and high oil yield (>32%), under hydrogen pressure of 50 kg cm^?1 in a nonhydrogen-donating solvent at 425°C for 60 min. Among the catalysts surveyed, Mo(CO)₆ gave the highest oil yield (57.7%) and the largest amount of hydrogen transferred to coal (3.1 wt.% of d.a.f. coal). However, the molybdenum and tungsten carbonyls did not exhibit high catalytic activity for low sulfur Wandoan coal in the absence of added sulfur. On the other hand, cobalt and nickel carbonyls showed high catalytic activity irrespective of the amount of sulfur in the reaction system. Fe(CO)₅Mo(CO)₆ binary catalyst promoted hydroliquefaction of Wandoan coal, resulting in increases in oil yield and transfer of hydrogen to coal in the presence of sulfur.     

Iron sulfate/sulfur-catalyzed liquefaction of Wandoan coal using syngas–water as a hydrogen source

Water-soluble iron sulfate/sulfur-catalyzed coal liquefaction using three kinds of hydrogen sources including syngas–water has been investigated. The liquefaction of Wandoan coal, an Australian subbituminous, with iron sulfate/sulfur as a catalyst precursor using syngas–water or carbon monoxide–water afforded higher coal conversions and oil yields than those using pressurized hydrogen gas. The pretreatment at relatively low temperature (200°C) was indispensable to achieve the high coal conversion. In the two-staged liquefaction (400°C, 60 min+425°C, 60 min), the use of syngas–water as a hydrogen source afforded higher coal conversion of 90.1% together with a high oil yield of 46.2% than those using pure hydrogen, and almost comparable to those using carbon monoxide–water, indicating the presence of synergistic effects of two hydrogen sources. At the early stage of the reaction, the contribution of carbon monoxide–water was predominant, whereas hydrogen gas significantly took effect at the latter stage. The XRD and XPS study revealed the formation of pyrrhotite, a possible active species, covered with a small amount of sulfate species.     

Hydroliquefaction of subbituminous coal Effectiveness of pretreatment by organic reduction with Na or k

Hydroliquefaction of subbituminous Taiheiyo coal, without any pretreatment and after organic reduction, was carried out in the presence of tetralin using fine iron powder as catalyst. Two pretreatment procedures were used (A) reduction of coal with Na in liquid ammonia solution and (B) treatment with K in refluxing THF. Samples of treated coal with well-dispersed iron powder were prepared by co-reduction of coal coated with FeBr₂ using both procedures. Non-catalytic liquefaction of coal treated by A showed double the yield of hexane-solubles compared with that from liquefaction of the original coal while non-catalytic liquefaction of the coal treated by B roughly tripled the hexane-solubles yield and consumed the same amount of hydrogen. The presence of iron powder increased hexane-solubles by 5 wt% while increasing benzene-solubles by 13 wt% compared with non-catalytic liquefaction of treated coal by procedure B. The coals prepared by co-reduction (A and B) showed highest conversion (73 and 77%) along with highest yield of HS (38 and 43%). This significant effect on hydroliquefaction could be correlated with a slight increase of hydrogen atoms added to coal organic materials and the loosening of clusters of aromatic sheets.     

Humic acid-Fe as catalyst for coal liquefaction

Research to increase the activity of iron based catalysts focuses on decreasing the particle size, increasing catalyst dispersion. The chelate compound of iron with humic acid (HA), which macromolecules radii can range from 6 to 50 nm, is truly in a highly dispersed state. Fe²⁺ or Fe³⁺ were dispersed finely into the HA matrix through the ion exchange with -COOH groups or chelate with carbonyl group in humic acid macromolecules. X-ray diffraction (XRD) and FT-IR spectrophotometer were used to characterize iron species before or after chelating with humic acid. The results indicate that there exist α-FeOOH, ferrihydrite and amorphous iron in HA-Fe. Most of the work has been conducted on a laboratory scale, and the results show that HA-Fe catalyst was approved for its excellent catalytic activity in coal liquefaction, and the conversion and oil yield of coal have been greatly improved.     

日本褐煤直接液化工艺

日本的BCL工艺是目前世界上唯一针对褐煤开发并经过了工业性试验结果（PP）验证的褐煤液化工艺,是先进成熟的直接液化工艺之一。改进的BCL工艺,由于采用了多级反应模式、双组分煤浆溶剂、高效催化剂、在线加氢等技术,使工艺的油收率进一步提高。     

Study on industrial catalyst for bituminous coal liquefaction

The catalyst activities and the grinding characteristics of natural iron compounds and sulfides were investigated with the aim of preparing an industrial coal liquefaction catalyst for the NEDOL process large-scale plants. From the viewpoint of economy, since these plants are to be located at coal mining sites, it is economical to utilize a natural compound produced in the vicinity of plant site as the catalyst raw material. The coal liquefaction, using an electromagnetic agitation type autoclave, suggested that iron sulfide (pyrite) is the best raw material for the catalyst, because it contains higher iron and sulfur for producing pyrrhotite, an active component under the reacting conditions, and thereby, it needs no pollutant sulfur addition. However, taking into consideration the grinding characteristics, iron sulfide is not thought to have good grinding characteristics in a fine particle zone. Co-pulverization, using iron sulfide and coal, improves the grinding efficiency, the abrasion and the catalyst activities, so that the industrial catalyst preparation can be realized by means of the co-pulverization method.     

Relative activity of transition metal catalysts in coal liquefaction

The catalytic activity of transition metals in coal liquefaction was studied and compared. Impregnation of coal with transition metals significantly increased oil production and asphaltene and preasphaltene conversion in coal liquefaction. Overall, coal conversion increased marginally and hydrocarbon gas production decreased slightly with metals. Iron impregnation was more active than cobalt, nickel, and molybdenum in preasphaltene conversion, whereas the other metals were more active than iron in asphaltene conversion. Hydrogen consumption decreased with all metals. The quality of generated solvent decreased with iron, but increased with other metals. Significant benefits were observed by using iron and molybdenum together; simultaneous impregnation of coal with iron and molybdenum significantly increased coal, asphaltene, and preasphaltene conversion, as well as oil production compared to individual metals. In addition, a mixture of iron and molybdenum decreased hydrocarbon gas production and increased hydrogen consumption and the quality of generated solvent over iron alone.     

煤炭直接液化油收率极限理论及其应用

首次建立了煤炭直接液化油收率极限理论,在指定的液化试验装置上,当催化剂、助催化剂和试验条件一定时,可以确定煤种的低限油收率和高限油收率,从而阐明了煤种进行直接液化主反应的限度,掌握煤种的低限油收率和高限油收率可以识别煤炭直接液化催化剂性能,最大限度地降低前沥青烯和沥青烯等液化反应中间产物的产率,就可以获得接近高限油收率的液化油收率。     

Hydroliquefaction of low-sulfur coals using iron carbonyl complexes—Sulfur as catalysts

Hydroliquefaction of low-sulfur Australian coals (Wandoan and Yallourn) was studied using iron carbonyl complexes as catalyst. The addition of Fe(CO)₅ (2.8 wt% Fe of coal) increased coal conversion from 48.6 to 85.2% for Wandoan coal, and from 36.7 to 69.7% for Yallourn coal in 1-methylnaphthalene at 425°C under an initial hydrogen pressure of 50 kg cm^?2. When molecular sulfur was added to iron carbonyls (Fe(CO)₅, Fe₂(CO)₉ and Fe₃(CO)₁₂), higher coal converions ( > 92%) and higher oil yields (>46%) were obtained, along with an increase in the amount of hydrogen transferred to coal from the gas phase (0.2 to 2.8%, d.a.f. coal basis). In the liquefaction studies using a hydrogen donor solvent, tetralin, Fe(CO)₅S catalyst increased the amount of hydrogen absorbed from the gaseous phase and decreased the amount of naphthalene dehydrogenated from tetralin. The direct hydrogen transfer reaction from molecular hydrogen to coal fragment radicals seems to be a major reaction pathway. Organic sulfur compounds, dimethyldisulfide and benzothiophene, and inorganic FeS₂ and NiS were found to be good sulfur sources to Fe(CO)₅. From X-ray diffraction analyses of liquefaction residues, it is concluded that Fe(CO)₅ was converted into pyrrhotite (Fe_1?xS) when sulfur was present, but into Fe₃O₄ in the absence of sulfur.     

原位担载型铁系煤直接液化催化剂的研究

考察了原位担载型铁基催化剂制备过程中,交换前驱体试剂ＦｅＣｌ３和Ｎａ２Ｓ的添加顺序对几种担载在不同煤表面上的催化剂性质的影响。研究结果表明,交换ＦｅＣｌ３和Ｎａ２Ｓ两种前驱体试剂的添加顺序,对不同煤种的液化效果产生不同程度的影响。这种民载体煤表面对离子的选择性吸附以及催化剂表面性质有关。     

Effect of process conditions on co-liquefaction kinetics of waste tire and coal

Thermal and catalytic liquefactions of waste (recycled) tire and coal were studied both separately and using mixtures with different tire/coal ratios. Runs were made in a batch tubing bomb reactor at 350–425°C. The effect of hydrogen pressure on the product slate was also studied. Mixtures of tire components and coal were used in order to understand the role of the tire as a solvent in co-liquefaction. In the catalytic runs, a ferric-sulfide-based catalyst impregnated in situ in the coal was used. Both the tire components and the entire tire exhibit a synergistic effect on coal conversion. The extent of synergism depends on temperature, H₂ pressure and the tire/coal ratio. Experiments with coal and tire components show that the synergistic effect of tire is due to the rubber portion of the tire and not the carbon black. The synergism mainly leads to an increase in the yields of asphaltenes, which are nearly double those in the coal-only runs at 400°C. The conversion of coal increases dramatically using the catalyst, but the catalytic effect is attenuated somewhat in the presence of tire, especially at high tire/coal ratios. The data were analyzed using a consecutive reaction scheme for the liquefaction of coal to asphaltenes and thence to oil+gas, both reactions being of second order; a second-order conversion of tire to oil+gas; and an additional synergism reaction when both coal and tire are present, first-order in both coal and tire. Parallel schemes were assumed for thermal (uncatalyzed) and catalyzed reactions. The uncatalyzed liquefaction of coal has a low apparent activation energy, 36 kJ/mol, compared to those for the synergism reaction (84 kJ/mol) and the catalytic coal liquefaction (158 kJ/mol). The conversion of asphaltenes to oil+gas is relatively independent of temperature and of the presence of the catalyst. The catalyst appears to play a significant role in the conversion of coal to asphaltenes, but a negligible role in the synergism reaction.     

超细FeS对五彩湾煤直接液化性能的影响

以硫酸亚铁为铁源,硫化钠为沉淀剂,采用液相沉淀法合成了超细FeS催化剂。以四氢萘为溶剂,反应温度430℃、氢初压6.0 MPa、反应时间60 min、溶煤比2∶1条件下,探讨超细FeS催化剂对五彩湾煤直接液化性能的影响。结果表明：硫酸亚铁基超细FeS粒子形貌均一,呈细棒状;五彩湾煤直接液化实验的油产率、液化率和转化率,以2.0%（wt,以活性金属元素计,相对于干燥无灰煤,下同）超细FeS为催化剂的实验分别达到56.15、73.29和81.21%（wt,相对于干燥无灰煤,下同）,高于相同条件下,以3.0%分析纯Fe2O3为催化剂的实验产率（分别是44.00、49.33和62.05%）。     

Effect of sulphur on coal liquefaction in the presence of dispersed iron or molybdenum catalysts

The effects of dispersed catalysts on coal liquefaction under hydrogen pressure were studied using small autoclaves. The catalysts were generated in situ by addition of elemental sulphur plus an oil-soluble carboxylic salt of either iron or molybdenum. Finely divided catalysts of relatively high activity were generated by this method. Residues isolated after liquefaction with added iron carboxylate and sulphur contained pyrrhotite, which is proposed to be the catalytically active species. The prime role of sulphur is to form pyrrhotite in combination with the iron. Addition of sulphur alone did not increase conversion. This method of catalyst preparation seems useful for further scientific study of the relationship between sulphur, metal sulphide catalysts and liquefaction activity.     

煤的一段加氢液化的催化剂

煤的一段加氢液化使用的催化剂有可弃性催化剂,铁和钼氧化物及溶于水或油的催化剂和浸渍催化剂,其中以Co-Mo/Al_2O_3,Ni-Mo/Al_2O_3和钼酸铵为最广泛;黄铁矿能促进煤向油的转化,但却降低了脱硫率:Fe(OH)3-MoO_3-S在较低和较高温度下都是一种较活泼的催化剂;SnMo混合物明显优于纯SnO_2或无助催化剂的MoO_3/Al_2O_3;硫化的Mo(CO)_6是一种性能很好的煤加氢液化催化剂。     

煤直接液化催化剂研究进展

我国煤炭储量丰富,煤液化制油技术是缓解我国一次能源结构中原油供应不足的措施。煤液化工艺的各种催化剂中,铁基催化剂以其高效、廉价及低污染而倍受青睐。非铁系催化剂有Sn和Zn水溶液、含碘的煤液化催化剂、碱金属氢氧化物或碳酸盐、Cr-Mo-Ⅷ族的加氢催化液化催化和硫转移剂等。概述了近年来煤液化技术在铁系催化剂研究、回收利用、制备工艺和预处理等方面的研究进展,综述了煤液化催化反应器研究状况。     

Properties and liquefaction activities of ferrous sulfate based catalyst impregnated on two Chinese bituminous coals

Activities of ferrous sulfate based catalysts impregnated on two Chinese coals were studied in coal liquefaction, and compared with an impregnated iron sulfide catalyst. Chemical forms and particle size distribution of the impregnated ferrous sulfate based catalysts were determined using EXAFS, XRD and SAXS techniques. The impregnated ferrous sulfate shows significant activity in the liquefaction of bituminous coals, but is less active than the impregnated iron sulfide catalyst. Addition of Na₂S or urea to the ferrous sulfate in the impregnation process increases the coal conversion to the level of the impregnated iron sulfide catalyst. Addition of Na₂S does not significantly promote the formation of iron sulfide on coal surface as usually believed. The iron impregnated on the coal surface existed mainly in the form of γ-FeOOH regardless of the forms of iron and the promoters. The most probable diameter of the impregnated ferrous sulfate based catalyst determined by SAXS is around 40-50 Å.     

Coal liquefaction using ore catalysts

Ores and ore concentrates containing minerals of Co, Mo, Ni, Fe, and other potentially active metals have been investigated as slurry catalysts for liquefaction of Blacksville mine, Pittsburgh seam, bituminous coal. The tests were conducted batchwise in a stirred autoclave for 30 min at 425°C and 13.79 MPa (2000 psig) hydrogen pressure according to a two-cycle scheme. In the first cycle, the reaction charge consisted of ground coal, catalyst, hydrogen, and SRC-II heavy distillate. The product of the first cycle was hot-filtered, and the liquid product served as a vehicle for the second cycle, which was otherwise run identically to the first. Reaction products from each cycle were analysed to determine conversion of coal, yield of liquids, liquid product viscosity, and group type (preasphaltene, asphaltene, and oil). Mixtures of ores containing iron pyrites and minerals containing other catalytically active transition metals were compared to pyrites alone and to a pulverized supported Co-Mo-alumina catalyst. An ore catalyst containing both Fe and Ni was superior to another that contained an equivalent mass of iron alone. The best ore catalysts tested, in terms of high liquid yields and low product viscosities, were mixtures of pyrites and molybdenum- and cobalt-containing ores. The latter yielded results that approached those obtained with an equivalent mass of cobalt and molybdenum on an alumina support.     

Production of bio‐crude from forestry waste by hydro‐liquefaction in sub‐/super‐critical methanol

Hydro‐liquefaction of a woody biomass (birch powder) in sub‐/super‐critical methanol without and with catalysts was investigated with an autoclave reactor at temperatures of 473–673 K and an initial pressure of hydrogen varying from 2.0 to 10.0 MPa. The liquid products were separated into water soluble oil and heavy oil (as bio‐crude) by extraction with water and acetone. Without catalyst, the yields of heavy oil and water soluble oil were in the ranges of 2.4–25.5 wt % and 1.2–17.0 wt %, respectively, depending strongly on reaction temperature, reaction time, and initial pressure of hydrogen. The optimum temperature for the production of heavy oil and water soluble oil was found to be at around 623 K, whereas a longer residence time and a lower initial H₂ pressure were found to be favorite conditions for the oil production. Addition of a basic catalyst, such as NaOH, K₂CO₃, and Rb₂CO₃, could significantly promote biomass conversion and increase yields of oily products in the treatments at temperatures less than 573 K. The yield of heavy oil attained about 30 wt % for the liquefaction operation in the presence of 5 wt % Rb₂CO₃ at 573 K and 2 MPa of H₂ for 60 min. The obtained heavy oil products consisted of a high concentration of phenol derivatives, esters, and benzene derivatives, and they also contained a higher concentration of carbon, a much lower concentration of oxygen, and a significantly increased heating value (>30 MJ/kg) when compared with the raw woody biomass. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Adsorptive Removal of Catalyst Poisons from Coal Gas for Methanol Synthesis

Abstract

As an integral part of the liquid-phase methanol (LPMEOH) process development program, the present study evaluated adsorptive schemes to remove traces of catalyst poisons such as iron carbonyl, carbonyl sulfide, and hydrogen sulfide from coal gas on a pilot scale. Tests were conducted with coal gas from the Cool Water gasification plant at Daggett, California. Iron carbonyl, carbonyl sulfide, and hydrogen sulfide were effectively removed from the coal gas. The adsorption capacities of Linde H-Y zeolite and Calgon BPL carbon for Fe(CO)₅ compared well with previous bench-scale results at similar CO₂ partial pressure. Adsorption of COS by Calgon FCA carbon appeared to be chemical and nonregenerable by thermal treatment in nitrogen. A Cu/Zn catalyst removed H₂S very effectively. With the adsorption system on-line, a methanol catalyst showed stable activity during 120 h of operation, demonstrating the feasibility of adsorptive removal of trace catalyst poisons from the synthesis gas. Mass transfer coefficients were estimated for Fe(CO)₅ and COS removal which can be directly used for design and scale up.     

Catalytic activity of iron compounds for coal liquefaction

The catalytic activity of pyrite and synthesized -FeOOH in coal liquefaction was investigated using batch autoclaves with the aim of developing an industrial iron catalyst. The results indicate that the presence of H₂S helps gaseous hydrogen transferring and prevents deactivation so that the catalyst promotes hydrocracking of coal and hydrogenation of the products. The activity converges with excess H₂S and sulfur addition equivalent to an S/Fe molar ratio of 2.0 being reasonable for the activation. The active site is located on the outer surface, with finely divided catalysts exhibiting high activity. Both pulverized pyrite and synthesized -FeOOH are sufficiently fine as to exhibit high activity in the process. Pulverized pyrite is an industrially feasible iron catalyst for coal liquefaction process, because it is inexpensive and does not require sulfur addition.