湿法烟气脱硫反应过程的实验研究

在石灰石/石膏湿法烟气脱硫中试台上,系统开展了浆液pH值、飞灰浓度、液气比、入口SO2浓度、烟气速度和氧化方式等对脱硫反应过程影响的实验研究。实验表明,脱硫效率随着石膏浆液pH值、液气比的升高而增加,且入口SO2浓度越高,液气比越低,影响效应越明显;脱硫效率随着烟气速度、烟气温度和入口SO2浓度的增加而下降;石膏浆液中飞灰含量对系统脱硫效率具有一定的促进作用:pH值>5.6,飞灰浸出液中Fe3+含量相对较低,Fe3+对脱硫反应过渡态催化氧化影响程度较轻,不同工况脱硫效率差别不大。pH值<5.6,飞灰浸出液中Fe3+含量随pH值降低而增大,增效效果逐渐显著;氧化方式对脱硫反应过程有明显的影响,强制氧化工艺的脱硫效率比自然氧化的高5%左右。     

氢氧化钠-钢渣双碱法烧结烟气脱硫工艺

在鼓泡反应器中考察了氢氧化钠-钢渣双碱法烧结烟气脱硫的主要影响因素。结果表明,在温度为常温,钢渣反应时间为2 h,钢渣加入量为40 g,SO2进口浓度为2 400 mg/m3,钢渣粒径为200目以上,烟气流量为0.05 m3/h,循环液pH保持在7～8,Na+浓度为0.5 mol/L,循环液为500 mL的条件下,脱硫率可长时间保持在80%以上。同时,对钢渣-氢氧化钠双碱法烧结烟气脱硫机理进行了探讨。     

活性炭纤维生物挂膜脱除硫化氢

生物脱硫法作为一种高效、高实用性的除硫新技术而受到越来越多的关注。以活性炭纤维为微生物载体,通过活性污泥上清液挂膜驯化,考察硫化氢进气量、喷淋量、pH值和硫酸根离子浓度等条件对脱硫效率的影响。研究结果表明,在室温下,硫化氢负荷为90 g/(m3.h),进气浓度控制在3 g/m3,进气量为60 L/h,喷淋量为250～650 L/(m3.d),pH为2～5的条件下,生物活性炭纤维对硫化氢的去除率可保持在98%以上。     

Advanced Concepts in FGD Technology: The SHU Process with Cooling Tower Discharge

The growing awareness of ecological issues in Europe, reinforced by the public debate surrounding acid rain, has led to the enactment of laws and regulations in West Germany relating to emissions from large coal fired combustors.

Flue gas desulfurization (FGD) units have been compulsory for new coal fired power plants in West Germany for about 12 years. The new legislation enacted in 1983, to be met by the middle of 1988, applies not only to new plants but, unlike in the United States, also to. existing power plants (>30MW).

The law currently specifies a residual SO2 emission level of 400 mg/Nm³ (0.311b MM/BTU) for large power plants (>100 MW), but a level of 200 mg/Nm³ (0.15 lb MM/BTU) is already under discussion in some cases. The legally binding emission standards stipulate that none of the daily averages, calculated on the basis of half hour averages may exceed the concentration allowed. SO2 removal efficiencies of 90 percent to 95 percent are normally provided. Since 1983, more than 35,000 MW of retrofit FGD units have been installed in Germany to meet this SO₂ standard.

The regulations also do not allow for the ponding of calcium sulfite scrubber sludge, but stipulate the production of gypsum from limestone slurry processes. Additionally the regulations require flue gases to have a minimum temperature in the stack of 72° C (162°F) after desulfurization. Treated flue gases do not have to be reheated if discharged via a cooling tower.     

Application of the Active Soda Process for Removing Sulphur Dioxide from Flue Gases

The active soda process1 was applied for desulfurlzatlon of flue gases emitted by a plant burning heavy fuel oil In a rotary drum drier for stone aggregate. The flue gas capacity of the plant was about 6,7 m³/s at normal conditions. The SO₂ concentration varied between 400– 500 ppm. The solid, dry and fine-grained NaHCO₃ of good quality was fed directly into the hot gas stream at the outlet of the rotary drier In two variants—with and without grinding. The mean particle size was 0.180 m^-3 or 0.070 m^-3, respectively. The achieved desulfurizatlon degree was shown to be directly dependent on the flue gas temperature and on the grinding effect, as well as on the normalized stoichiometric ratio. The highest achieved desulfurization degree amounted up to 74 percent. During the design of the desulfurization process no pilot plant installations and tests were necessary, and for the final process no special chemical reactor was used.     

空速和二氧化碳对沼气脱硫剂硫容确定的影响

为了弄清空速与二氧化碳含量对氧化铁脱硫剂硫容确定的影响,分别在实验气源为纯硫化氢,空速为40、80、120和160 h-1以及实验气源为二氧化碳含量分别在0%、20%、40%和80%,其余为硫化氢,空速为80 h-1条件下,对T502(粗脱硫剂)和HXT-2(精脱硫剂)2种氧化铁脱硫剂进行了不同测试条件对氧化铁硫容确定影响的研究。研究结果表明,T502和HXT-2氧化铁脱硫剂硫容测试结果随着空速和二氧化碳含量增加而减少,结果显示了在空速较低条件下(120h-1),二氧化碳含量在40%以下时对氧化铁脱硫剂硫容测试结果影响不大,但二氧化碳含量在40%以上时,对氧化铁脱硫剂硫容测试结果影响显著。     

Effect of potassium hydroxide activation in the desulfurization process of activated carbon prepared by sewage sludge and corn straw

Series sludge straw–based activated carbons were prepared by sewage sludge and corn straw with potassium hydroxide (KOH) activation, and the desulfurization performance of activated carbons was studied. To obtain the best desulfurization performance, the optimum ratio between the raw materials and the activator was investigated. The results showed that when the mass ratio of sewage sludge, corn straw, and KOH was 3:7:2, the activated carbon obtained the best breakthrough and saturation sulfur sorption capacities, which were 12.38 and 5.74 times, respectively, those of samples prepared by the nonactivated raw materials. The appropriate KOH could improve the microporosity and alkaline groups, meanwhile reducing the lactone groups, which were all beneficial to desulfurization performance. The chemical adsorption process of desulfurization can be simplified to four main steps, and the main desulfurization products are elemental sulfur and sulfate.

Implications: Sewage sludge (SS) and corn straw (CS) both have great production and wide distribution and are readily available in China. Much attention has been paid on how to deal with them effectively. Based on the environment protection idea of waste treatment with waste and resource recycling, low-cost adsorbents were prepared by these processes. The proposed method can be expanded to the municipal solid waste recycling programs and renewable energy plan. Thus, proceeding with the study of preparing activated carbon by SS and straw as a carbon-based dry desulfurization agent could obtain huge social, economic, and environmental benefits.     

Desulfurization of Caribbean Fuel

An American Petroleum Institute study of desulfurization of Caribbean fuel oil was completed in February 1967. The report is unique in that proprietary information was made available to the contractor, the Bechtel Corp., by task force members and licensors of desulfurization processes. Thus confidential information never before available to a single organization was used to develop feasibility and incremental costs of various processes for desulfurization. The report provides needed guideposts for decision-making by governmental units as well as by industry. Incremental costs are presented for intermediate levels of desulfurization from the normal level for Caribbean heavy fuel oil of 2.6% down to 0.5%, as well as the sensitivity of costs to sulfur credits and to rate of recovery of invested capital. Degree of justifiable confidence in the various data is discussed. Effects of desulfurization on other characterisics of the fuel oil are also discussed.     

Fenton氧化法同时脱硫脱硝的实验研究

应用Fenton液相氧化吸收法进行同时脱硫脱硝实验。首先,利用单因素实验,分别考察了H2O2浓度、Fe2+投加量、初始pH值、UV照射和温度对脱硫脱硝的影响。结果表明,SO2和NO去除率随着H2O2浓度和Fe2+投加量的增大而提高;初始pH对SO2和NO的去除有较大影响;UV能促进SO2和NO的净化;温度对脱硫效率影响不大,但对NO的去除有显著作用,适当升温可以提高脱硝效率。随后,考察了SO2对NO去除率的影响。通过单独脱硝和同时脱硫脱硝的对比实验发现,SO2的加入对NO的去除有一定的促进作用,Fenton法可同时获得起始约80%的脱硝效率和98%以上的脱硫效率。     

废轮胎热解衍生油非加氢脱硫

衍生油是废轮胎热解过程中最重要的产品之一,其最有意义的一种用途是作为燃料来得到较高的附加值.但是衍生油的硫含量较高,且具有恶臭味道,妨碍了它作为燃料的广泛应用.在管式反应器上分别考察了氧化锌、混合脱硫剂、A.D.A和MDEA+环丁砜法对废轮胎高温热解气的非加氢脱硫效果,并对不同的脱硫工艺作了简要的经济评价.结果发现,白土、陶土和石灰粉混合脱硫剂与氧化锌的热解气直接脱硫效果较好,衍生油的硫含量可降低到0.11％左右.采用油气分离的A.D.A脱硫工艺最经济.     

Economics and Alternatives for Sulfur Removal from Coke Oven Gas

Two processes are currently being employed in North America for the desulfurization of coke oven gas, the Vacuum Carbonate System, and the Stretford System. A third, the Sulfi-ban Process, which was recently announced, now has several plants scheduled for construction. Overall operating requirements for each of these processes are considered in detail. Emphasis is placed on an identification of power and steam requirements, the types and amounts of solid and/or liquid waste streams produced together with methods for their treatment, and the net desulfurization efficiencies achieved by each process. Detailed estimates of capital and operating costs for desulfurization are considered, and equipment needs for environmental control requirements are discussed.     

烧结烟气脱硫剂性能的研究

为了提高脱硫效率和合理利用烧结过程中产生的机头灰,在半干法烟气脱硫剂生石灰中,加入一定量的烧结机头灰作为脱硫催化剂。在测定机头灰与生石灰化学成分、粒度和比表面积的基础上,研究和分析了机头灰与生石灰的质量配比对于脱硫效率的影响。结果表明,脱硫剂与机头灰在粒径分布和比表面积上都较接近,但经过消化活化后的混合脱硫剂的比表面积明显增大。当机头灰添加量为脱硫剂质量的2%～5%时,脱硫效率提高了2%～3%。机头灰与生石灰的胶凝反应以及机头灰中Fe2O3的催化作用是主要的作用机理。     

Effect of Flue Dust on the Vanadium Oxide Catalyst Utilized by the Contact Oxidation Process

Concepts for controlling SO₂ from fossil fuels can be separated into two main categories: (1) Residual and vacuum gas oil desulfurization and (2) Flue gas desulfurization. The Kiyoura-T.I.T. process confines itself to the desulfurization of flue gas. It employs vandium oxide as a catalyst which oxidizes the sulfur dioxide to trioxide, followed by a gaseous phase reaction of ammonia. The end product, ammonium sulfate is removed by an electrostatic precipitator. (The details were presented at annual meetings of APCA in 1966 and 1967 as 1 and II.) Flue gas is passed through cyclone and dust filter to remove dust. Under normal operating conditions almost all of the dust is removed at the filters. The author carried out experiments to determine whether there was any effect on the activity of the catalyst, assuming that a portion of the dust escapes into the stream along the flue. It has been generally accepted that in fuel oil firing steam power plants, about 100 mg./nm³ of dust including carbon, hydrocarbon, and ash are normally contained in the flue stream. The carbon and hydrocarbon is oxidized readily at the filters and exists only as ash. An amount of ash equivalent to the amount assumed to have settled on the catalyst over a period of 3–12 months, was placed on the catalyst, and experiments were carried out. The SO₂ conversion efficiency was measured and found to be over 93%. The results showed that at the actual operational temperature of 450°C, ash had practically no effect at all.     

气升式反应器中微生物烟气脱硫研究

基于微生物酸性铁溶液烟气脱硫特性,实验构建了一套内循环气升式反应器.在反应器中,利用处于对数生长期的氧化亚铁硫杆菌(Thiobacillus ferrooxidans)酸性铁溶液进行了模拟烟道气SO2脱除实验研究.为寻求高脱硫率,实验研究了铁离子浓度、入口氧含量、细菌数和pH值的变化对脱硫率的影响.考察了反应液中Fe(Ⅱ)离子浓度的变化规律.实验表明,含T.f菌酸性铁溶液的脱硫效果较高;Fe离子浓度在7.67 g/L左右时脱硫率最佳;入口气中氧含量、反应液中细菌数和pH值越高,反应液的脱硫率也就越高.反应液中的Fe(Ⅱ)离子浓度是一先扬后抑的变化过程.     

Thiosulfate as an Oxidation Inhibitor in Flue Gas Desulfurization Processes: A Review of R&D Results

Sodium thiosulfate (Na₂S₂O₃) has been tested in a pilot plant as an oxidation inhibitor in flue gas desulfurization by lime and limestone slurry scrubbing with and without MgO and adiplc acid additives. The effectiveness of thiosulfate is proportional to the inhibitor product, defined as the product of thiosulfate concentration (M), calcium concentration (M), and the moles of SO₂ absorbed per hour per liter of hold tank volume. Gypsum saturation was less than 100 percent and scaling was eliminated when the inhibitor product exceeded 0.3 × 10^?6(gmol/L)³/h. Thiosulfate was relatively more effective in systems with chlorides and less effective in systems promoted by MgO. An inhibitor product greater than 10^?6(gmol/L)³/h significantly enhanced dewatering of solids from limestone scrubbing. SO₂ removal and/or limestone utilization were increased in systems that started with less than 10 mM dissolved calcium.     

络合铁法脱除垃圾填埋气中的H2S

建立了以EDTA和柠檬酸为铁盐络合剂的循环脱硫体系,采用络合铁法对垃圾填埋气中的H₂S进行脱硫中试实验,结果表明实验所建立的络合铁脱硫体系运行稳定,脱硫效率高,适合应用于垃圾填埋气中硫化氢脱除。     

Sulfur and Carbon Cycling in a Flue Gas Desulfurization Sludge Disposal Site

Abstract

Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial δ¹³C 3.2–3.8‰), gypsum (initial δ³⁴S 7.6–8.6‰), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-δ³⁴S sulfide, consuming organic carbon and generating low-δ¹³C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has δ³⁴S near 6‰, and calcite has δ¹³C as low as -1.7‰; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of bacterial reduction. After the pond is abandoned, these products may adversely affect attempts to revegetate the site. Future bacterial reduction may be best controlled by dewatering and limiting the supply of organic matter in percolating surface water.     

基于响应曲面法优化烧结烟气脱硫灰改性工艺

采用BOX-Behnken的中心组合实验设计及响应面分析方法对半干法烧结烟气脱硫灰进行改性研究,得到脱硫灰转化率的预测模型。结果表明:通过该预测模型可以很好地描述脱硫灰的转化率与反应温度、反应时间和气固比等重要操作参数之间的关系,R2=0.9903。因素分析表明,反应温度对脱硫灰的转化率影响最大,同时反应温度和气固比的交互作用与反应温度和时间的交互作用对脱硫灰的转化率的影响作用相同。利用得到的改进预测模型可以计算脱硫灰的转化率。     

ORP as slurry oxidation index and model modification in wet desulfurization system

ABSTRACT

Due to wet desulfurization system lacks effective control indicators for the oxidation process, so the sulfite oxidation in the slurry and the quality of gypsum become unstable. In this paper actual desulfurization system operation data are used to improve the ORP semi-empirical formula obtained in the laboratory. It was concluded that the ORP was mainly affected by the concentration of sulfite and pH during the operation of the actual desulfurization system, the dissolved oxygen was less affected by the small concentration change during operation. It is verified that the model can correct the ORP measurement value by using other conventional measurement data from the power plant. The results can provide theoretical support for adding ORP as a control index to optimize the oxidation process.     

用于气态零价汞转化的催化剂研究

零价汞的高效去除是燃煤烟气汞污染控制过程中的关键环节。为了促进烟气中的零价汞转化为易于去除的氧化态汞,分别考察了在有HCl存在时,几种过渡金属氧化物(Cu、Fe、Mn、Co和Zr)对零价汞氧化的催化作用,以筛选出性能较好的催化组分;为提高催化剂的抗SO2性能,分别尝试了利用几种金属元素(Sr、Ce、W和Mo)对催化剂进行掺杂改性的方法。结果表明,锰氧化物的催化作用最好,其最佳使用温度在573 K左右;SO2对零价汞的催化氧化有明显抑制作用,在无SO2及1 400 mg/m3SO2时锰催化剂对零价汞催化氧化效率分别为93%和78%。而Mo改性的锰氧化物催化剂的抗硫性能大幅提高,在1 400 mg/m3SO2存在的情况下其对零价汞的催化氧化效率可达到90%以上,较其他改性元素高。