流场对MEC生物阴极CO2还原性能与产物的影响

针对微生物电解池 （microbial electrolysis cell,MEC）CO₂还原过程阴极CO₂还原速率低的问题,本文通过改变阴极室的流场环境,探究流场对生物阴极启动、运行、产物及功能微生物的影响,阐明MEC生物阴极CO₂还原性能、产物转化、微生物群落对流场的响应关系。结果表明,流场不仅增强了生物阴极还原CO₂能力（电子消耗量提高了10%,其中CO₂产乙酸途径消耗电子量提高了30%）,还使生物阴极的CO₂还原途径由启动阶段的CO₂还原产甲烷转变为运行阶段产乙酸。高通量分析表明,流场改变了生物阴极和阴极液的微生物群落结构,使阴极生物膜的嗜氢型产甲烷菌（Methanobacterium）向嗜乙酸型产甲烷菌（Methanosaeta）主导的群落演变。产乙酸菌群落（Petrimonas、Candidatus_Caldatribacterium）丰度较对照组提高了3.8%,在CO₂产乙酸过程中起到重要作用。本研究可为MEC还原CO₂产乙酸的定向调控研究提供理论和技术支撑。     

脱硫菌磁化培育及生物浸出脱除煤中黄铁矿硫的研究

将磁化技术用于煤炭脱硫菌种的培育，研究了磁化培育下的中国煤系与非煤系氧化亚铁硫杆菌对煤中黄铁矿硫的脱除效果。研究表明，磁化环境对矿质化学营养脱硫菌氧化亚铁硫杆菌的生长具有促进作用，一定磁化培育条件下的煤系氧化亚铁硫杆菌对小于0．075mm的煤样浸出24d的最大脱硫率（86．16％）高于非煤系氧化亚铁硫杆菌的最大脱硫率（82．56％），磁化培育下的煤系氧化亚铁硫杆菌具有更好的脱除煤中黄铁矿硫的效果。     

ZrO2/SiO2催化剂的制备及其氧化脱硫性能研究

以己内酰胺-八水氧氯化锆低共熔溶剂为添加组分,采用溶胶-凝胶法合成含锆的硅胶,再经过高温煅烧得到n-ZrO₂/SiO₂ （n=2%,4%,6%） 负载型催化剂。并用红外光谱（FT-IR）、X射线衍射（XRD）、扫描电镜（SEM）、N₂吸附-脱附、X射线光电子能谱（XPS）对其进行结构表征,确定ZrO₂成功负载到SiO₂上。以ZrO₂/SiO₂为催化剂和吸附剂,H₂O₂为氧化剂组成催化氧化脱硫体系,并应用于模拟油脱硫。分别考察了氧化锆负载量、反应温度、氧硫比、催化剂加入量及不同类型的硫化物对脱硫效果的影响。实验结果表明,在反应温度为70℃、n（H₂O₂）/n（S）=4（摩尔比）、4%-ZrO₂/SiO₂的加入量为0.2 g的最佳反应条件下,氧化脱硫体系对二苯并噻吩（DBT）、4,6-二甲基二苯并噻吩（4,6-DMDBT）和苯并噻吩（BT）的脱除率分别为98.7%、93%和65.9%。且4%-ZrO₂/SiO₂回收利用5次后,DBT脱除率仍可达到91.8%。     

NHD/MDEA/H2O复合脱硫液催化水解羰基硫

为解决传统湿法脱硫工艺中有机硫脱除效率低、副产物多等问题,依托配方型溶剂脱硫工艺,以聚乙二醇二甲醚（NHD）、N-甲基二乙醇胺（MDEA）和水为原料构建新型湿法催化水解羰基硫（COS）脱硫体系。优化复配溶剂组成比例,确立配方溶剂组成为25% MDEA/15% H₂O/60% NHD,考察了脱硫操作参数、反应温度、气体浓度、气体流量等因素对脱硫的影响,使用气相色谱和离子色谱分析探究脱硫过程及反应动力学。结果表明,在低温（298.15~343.15 K）、常压条件下对COS的脱除效率达80%以上;复配溶液将吸收后的COS催化水解为H₂S和CO₂,吸收过程符合准一级反应动力学。该脱硫液中有机溶剂含量占85%以上,可解决脱硫副产物产生多和碱耗大的问题,是一种新型有机介质脱硫工艺。     

阴离子对铁盐氧化脱除煤中硫的影响

采用Fe（NO₃）₃、Fe₂（SO₄）₃和FeCl₃溶液氧化脱除山西某焦煤中的硫,研究铁盐种类及添加无机酸对脱硫效果的影响,并利用红外光谱仪对处理前后的煤样进行表征。结果表明,Fe（NO₃）₃的脱硫效果远高于Fe₂（SO₄）₃和FeCl₃;溶液中添加H₂SO₄和HCl会抑制Fe³⁺的氧化脱硫效果;较低浓度的HNO₃促进Fe（NO₃）₃氧化脱除煤中的FeS₂和硫醇、硫醚等有机硫,而高浓度的HNO₃又会抑制Fe³⁺与FeS₂反应,致使脱硫率下降。     

国外煤炭燃前脱硫综述

<正> 一、微生物脱硫能够应用于煤脱硫领域的微生物种类很多,目前广泛采用的是硫杆菌属的氧化亚铁硫杆菌和氧化硫硫杆菌。Brierly 于70年代末期从酸性热温泉和富硫土壤中分离出了嗜热铁氧化菌。80年代末,美国大西洋研究公司成功地从自然生物种群中分离出了 CB1和CB2,这两种微生物对脱除煤中的噻吩硫等有机硫有特效。国外微生物脱除煤中无机硫的研究十分     

改进型脱硫溶剂DS05—2在天然气有机硫脱除的应用

延长石油天然股份有限公司为应对未来井口气组份变化,更好满足企业天然气事业发展需要,联合醇胺产品生产企业—江苏苏太湖新材料控股有限公司进行了天然气有机硫脱除工业化中试试验,以实现天然气中H₂S脱除的同时、部分CO₂和少量有机硫。实验表明：改进型脱硫溶剂DS05-2,在保证净化气硫化氢达标的同时,较好地脱除了原料天然气中CO₂和有机硫,提高气体净化质量,有较好的推广应用价值。     

富氧燃烧烟气净化工艺研究进展

随着工业的快速发展,化石燃料消耗与日俱增,造成了大量温室气体CO₂的排放,全球气候变化形势不容乐观。为了减少CO₂排放,需要对高浓度CO₂进行捕获、利用与封存,而富氧燃烧技术能有效实现碳捕集,是目前最具潜力的碳减排技术之一。富氧燃烧过程中,SO_x、NO_x、Hg等污染物以及惰性气体的存在不利于碳的捕集与封存。烟气中各成分浓度会对管道运输、地质储存和提高采收率(EOR)产生影响,介绍了烟气中CO₂及各种杂质浓度的不同标准,系统综述了国内外脱硫、脱硝、脱汞和惰性气体脱除以及联合脱除技术的研究进展。脱硫部分除介绍传统脱硫技术外,重点描述了富氧燃烧烟气中CO₂气氛对SO_x脱除的影响以及加压条件下SO₂的转化与去除。发现CO₂气氛下SO₂的吸收速率相比N2气氛有所降低,且SO₂吸收过程中临界pH发生变化。脱硝部分重点描述了氧化吸收法脱硝技术以及加压条件下NO的氧化机理,并对高压下NO的氧化动力学进行阐述。随着压力的增加,NO氧化速率常数呈先下降后上升的趋势,且证明了反应器压力对液体夹带率的影响比较显著。总结了Hg脱除技术中不同烟气成分对Hg氧化的影响,HCl与Cl2起到了明显的促进作用。对活性炭进行改性,增加孔结构比表面积以及吸附剂表面的活性位点,提高Hg的脱除效率。介绍了惰性气体的净化技术,主要采用变压吸附方法来吸附和解吸附,降低了CO₂气流中惰性气体去除的成本,实现一部分惰性气体再次循环回到锅炉中,提高CO₂的捕获。重点讨论了在烟气压缩液化系统中的联合脱除技术,有效利用压缩过程条件将SO_x、NO_x、Hg分别以硫酸、硝酸、Hg(NO₃)₂形式协同去除,随着压力的增加,SO_x与NO_x去除效率提高,有利于SO₄^-2、NO₃^-、HADS和HAMS(N-S化合物)的生成,同时也导致了N2O生成量增多。证明了Hg与NO₂是气相反应,提出了高压下NO₂与Hg反应产物的不确定性。简单介绍了低温碳捕集技术,有潜力取代洗涤器和其他烟气处理方法,但目前还缺乏可行性的研究。未来需对不同压力下NO氧化速率常数的变化趋势进行解释,高压下NO_x与SO_x联合脱除的产物以及NO₂与Hg的反应产物进行分析。     

碳酸钠浓度对废电池铅膏脱硫影响机制与动力学

以铅膏为研究对象,采用碳酸钠为脱硫剂,系统研究了碳酸钠浓度对铅膏脱硫率及铅收得率的影响,并借助化学分析、扫描电镜分析仪（SEM-EDS）、X射线衍射分析仪（XRD）揭示了铅膏脱硫反应机理,计算了动力学参数。结果表明,铅膏脱硫率随碳酸钠浓度的增加而增大,而铅收得率变化规律相反。铅膏主要由硫酸铅及铅的氧化物组成。在碳酸钠浓度小于0.150 mol/L时,脱硫产物中主要以PbCO₃和Pb₃（CO₃）₂（OH）₂形式存在;随着浓度的增加,PbCO₃不断向Pb₃（CO₃）₂（OH）₂转化,并最终转化为NaPb₂（CO₃）₂（OH）₂,导致铅收得率降低。铅膏脱硫过程活化能随浓度的增大而减小,受化学反应控制。浓度低于0.208 mol/L时,活化能降低幅度较大,由7.275 kJ/mol降至5.312 kJ/mol,之后活化能随浓度的增加变化程度较小。     

等速升温流态化下CaO/生物质焦的SO2/NO联合脱除特性

燃煤锅炉污染物超低排放标准对电厂脱硫和脱硝系统提出了更高的要求。CaO作为脱硫剂可以实现循环流化床锅炉烟气中SO₂的高效脱除,焦炭作为还原剂直接还原NO,同时CaO的存在对焦炭还原NO起催化作用,可以实现燃煤烟气中SO₂/NO的联合脱除。为了探究连续温度变化对CaO/生物质焦联合脱硫脱硝性能的影响,在钙循环捕集CO₂技术背景下,研究了等速升温流态化下CaO/生物质焦的SO₂/NO联合脱除特性。探究了烟气中O₂和CO₂对CaO/椰壳焦脱除SO₂/NO的影响。结果表明,O₂通过对椰壳焦表面碳原子的活化作用降低了异相还原NO温度,在300~950℃等速升温过程中CaO/椰壳焦的NO脱除效率逐渐增加,780℃以上能实现100%脱硝。O₂也提高了CaO/椰壳焦的脱硫效率。CO₂与CaO的碳酸化反应以及与椰壳焦的气化反应对同时脱除SO₂/NO有明显抑制作用。O₂和CO₂共同作用下,在500~800℃内CaO/椰壳焦的脱硝效率随温度升高而增加,脱硫效率先降低后升高。NO促进了CaO/椰壳焦脱除SO₂,而SO₂对脱硝有抑制作用。800℃时CaO/椰壳焦同时脱除SO₂和NO的效率分别为97.7%和93.9%。     

Microbial desulfurization of coal by Thiobacillus ferrooxidans and thermophilic archaea

Several different microorganisms have been suggested for coal desulfurization. In the present investigation, the thermophilic archaea Acidianus brierleyi (DSM 1651), Sulfolobus acidocaldarius (DSM 639) and Sulfolobus solfataricus (DSM 1616) were compared with the mesophilic bacterium Thiobacillus ferrooxidans (DSM 583) concerning their capability of removing sulfur from coal. The desulfurization rate as well as the amount of sulfur removed by the microorganisms was studied.

Two of the investigated microorganisms, Thiobacillus ferrooxidans and Acidianus brierleyi, were capable of oxidizing pure pyrite as well as oxidizing sulfur in coal. A kinetic analysis was performed assuming first order reactions. The rate constant for oxidation of pure pyrite by A. brierleyi was observed to be higher than for T. ferrooxidans. The values of the rate constants for sulfur removal from coal were comparable for the two microorganisms, but were higher than for oxidation of pure pyrite.     

Bioenergetics of the metal/sulfur-oxidizing extreme thermoacidophile, Metallosphaera sedula

Identification of more effective biocatalysts than Thiobacillus ferrooxidans has been of interest for the optimization of biological removal of inorganic sulfur from coal. The recently isolated thermoacidophile, Metallosphaera sedula, leaches metal sulfides at rapid rates and could be a feasible biocatalytic alternative for such use. The bioenergetic and biocatalytic features of M. sedula as they apply to metal leaching, with particular attention to coal pyrite oxidation, are currently being evaluated. The questions examined include

1. (1) how does M. sedula compare with other microorganisms with similar bioleaching capabilities,

2. (2) how do inorganic energy substrates factor into M. sedula's metabolic scheme, and

3. (3) how can higher metal leaching rates be achieved with M. sedula?

To answer these questions, the relation between the organism's metabolic energy sources (sulfur, iron pyrite, organic compounds) and intracellular energy-requiring reactions is being studied. It is hoped that this framework can be used to evaluate and improve the various microbial options for inorganic sulfur removal from coal.     

An evaluation of autotrophic microbes for the removal of carbon dioxide from combustion gas streams

Carbon dioxide is a greenhouse gas that is believed to be a major contributor to global warming. Studies have shown that significant amounts of CO₂ are released into the atmosphere as a result of fossil fuels combustion. Therefore, considerable interest exists in effective and economical technologies for the removal of CO₂ from fossil fuel combustion gas streams. This work evaluated the use of autotrophic microbes for the removal of CO₂ from coal fired power plant combustion gas streams. The CO₂ removal rates of the following autotrophic microbes were determined: Chlorella pyrenoidosa, Euglena gracilis, Thiobacillus ferrooxidans, Aphanocapsa delicatissima, Isochrysis galbana, Phaodactylum tricornutum, Navicula tripunctata schizonemoids, Gomphonema parvulum, Surirella ovata ovata, and four algal consortia. Of those tested, Chlorella pyrenoidosa exhibited the highest removal rate with 2.6 g CO₂ per day per g dry weight of biomass being removed under optimized conditions. Extrapolation of these data indicated that to remove CO₂ from the combustion gases of a coal fired power plant burning 2.4 × 10⁴ metric tons of coal per day would require a bioreactor 386 km² × 1 m deep and would result in the production of 2.13 × 10⁵ metric tons (wet weight) of biomass per day. Based on these calculations, it was concluded that autotrophic CO₂ removal would not be feasible at most locations, and as a result, alternate technologies for CO₂ removal should be explored.     

Bioleaching of molybdenum from coal liquefaction catalyst residues

It has been shown that the bacterium Thiobacillus ferrooxidans can solubilize MoS₂ from coal liquefaction catalyst residues. The MoS₂ is formed during the liquefaction process from a molybdenum catalyst precursor. MoS₂ is insoluble; in order to be recovered and reused, it must be converted to a soluble form. T. ferrooxidans can oxidatively solubilize the molybdenum in MoS₂ to molybdate, in which form it can be recovered as a soluble or HCl extractable material. Bioleaching experiments show that with a starting cell concentration of 1.0 × 10⁷ cells ml⁻¹, or greater, a significant amount of the molybdenum in the residue was solubilized. These experiments indicate that the amount of molybdenum biologically solubilized from the liquefaction residues is dependent on inoculum size, with all strains of T. ferrooxidans tested having equal ability, and on the particle size of the residue. An important factor in the solubilization of MoS₂ by T. ferrooxidans is the inhibitory effect of molybdate. Literature reports that as little as 10 ppm molybdate is inhibitory to growth or ferrous iron oxidation. However, leachates containing in excess of 70 ppm molybdenum (equivalent to 116 ppm molybdate) were generated as a result of bioleaching of the liquefaction residue. When cells from previous leaching experiments were used to inoculate flasks containing fresh media and additional liquefaction residue, the bacteria were able to bioleach the fresh residue. Recent experiments have focused on the ability of T. ferrooxidans to produce protective agents in the leachate that minimize the inhibitory effects of molybdate. We found that production of the protective factor(s) did not depend on previous exposure of the cells to molybdenum or liquefaction residue.     

活性碳纤维负载型脱硫剂在矿井气体环境条件下的应用

H₂S作为煤炭开采过程中经常会出现的气体,对煤矿的生产安全造成不利影响,必须进行脱除工作。然而煤矿中还可能存在其他组分的气体,这些气体可能会一定程度上影响H₂S的脱除。本文选取活性碳纤维分别负载氢氧化钠及氧化铜,并选取两种材料的最佳负载量。之后,模拟煤矿实际条件,探讨复合脱硫剂在实际矿井气氛条件下的脱硫性能。结果表明,煤体在受热情况下会产生的多组分混合性气体,这些气体会对脱硫剂性能产生极大的影响,当煤体温度升高,其产生的CO、CO₂等气体呈指数增大,并且会产生少量的CH₄、C₂H₆、C₂H₄、C₂H₂等气体,随着这些气体生成量增大,脱硫剂脱硫性能开始下降。且在矿井气体氛条件下SO₂气体的产生受到了抑制,特别在煤气组分含量大的情况下,SO₂气体甚至晚于H₂S气体出现。此外通过测量脱硫剂失活后的表面pH,发现即便在一些气体氛围下脱硫剂的脱硫时间更短,其脱硫后产物的表面pH极为相近,说明煤体产生的酸性气体CO以及CO₂等可能也被吸附到脱硫剂的表面上生成酸性物质。     

Desulfurization of coal by air + steam at 400°C in a fixed bed

A high-volatile coal was treated by mixtures of air and steam at 400°C. The coal particle size, air/steam ratio and treatment time were varied. The degree of conversion of total sulfur depended on the particle size (but not proportionally) and the air/steam ratio (proportionally). The kinetics of the heterogeneous desulfurization by oxidation of FeS/FeS₂ was investigated. The kinetic data were well described by the model of an unreacted shrinking core in a coal particle of unchanging size. The coal particle size affected the external and internal diffusion of O₂ molecules only; the air/steam ratio affected the internal diffusion of O₂ molecules only. On average, the process was governed 14% by external diffusion, 76% by internal diffusion and 10% by chemical reaction. It was possible to elucidate the desulfurization mechanism merely from a knowledge of the experimental relation between total sulfur conversion degree and treatment time.     

基于热重-质谱联用的煤粉富氧燃烧动力学及污染物生成特性

富氧燃烧是最具工业化前景的燃烧中碳捕集技术之一,为更深入掌握煤粉富氧燃烧的着火模式和污染物生成特性,本文构建了热重-质谱联用实验系统,以烟煤和无烟煤标准煤样为对象,针对3个不同的氧气体积分数：21%、30%和50%,研究了O₂/Ar和O₂/CO₂气氛下煤粉的富氧燃烧特性。结果表明,O₂/CO₂气氛下煤粉着火温度和燃尽温度均降低,燃烧速率提高,燃烧时间缩短;两种煤粉在O₂/Ar气氛下的燃烧都属于非均相着火,而富氧燃烧都属于均相着火模式;氧气体积分数在30%以上时,无烟煤O₂/CO₂燃烧的表观活化能明显低于O₂/Ar气氛,在相同工况下烟煤的表观活化能均低于无烟煤;O₂/CO₂气氛促进了CO和挥发分NO的逸出,生成温度均低于O₂/Ar气氛,CO会对NO起到还原作用。     

O2/CO2气氛对准东煤灰熔融行为和微观理化特性的影响

近年在新疆准东地区探明了储量巨大的准东煤,而O₂/CO₂燃烧技术被认为是最有前景的碳捕集技术之一,因此研究准东煤的O₂/CO₂燃烧技术对中国煤炭的大规模高效清洁安全利用具有重要意义。然而目前鲜有O₂/CO₂气氛对准东煤灰熔融行为和微观理化特性影响的相关研究。因此针对准东煤,利用灰熔点测定仪、SEM-EDS分析开展相关研究。实验结果表明：空气气氛、CO₂气氛及O₂/CO₂气氛的转变对准东煤灰熔融温度的影响可以忽略不计,但会在一定程度上改变煤灰的微观理化特性。O₂/CO₂气氛主要影响到煤灰表面Ba、Na和Ca元素的分布,而O₂浓度是影响准东煤灰表面微观形貌的主要因素。     

DECOMPOSITION BEHAVIOR AND MECHANISM OF CALCIUM SULFATE UNDER THE CONDITION OF O2/CO2 PULVERIZED COAL COMBUSTION

The decomposition behavior and mechanism of calcium sulfate in O₂/CO₂ pulverized coal combustion were studied in an entrained flow reactor. A reaction rate expression correlating the influence of various factors was proposed for CaS0₄ decomposition and it is able to predict CaS0₄ decomposition satisfactorily. Under the conditions investigated, the decomposition of CaS0₄ was found to be a regime of chemically controlled shrinking core reaction. A CO₂-rich atmosphere enhances CaSO₄ decomposition in absence of oxygen. CaSO₄ particles have catalytic effect on formation of CO from CO₂. A high SO₂ concentration inhibits CaSO₄ decomposition. The kinetics of CaSO₄decomposition has obvious dependence on experimental facilities and conditions, whereas the activation energy has much lower dependence. The kinetics derived in this work is more appropriate for investigating desulfurization in O₂/CO₂ pulverized coal combustion because an entrained flow reactor has a much closer condition to that in O₂/CO₂ pulverized coal combustion than a TGA.