Tài liệu Mechanism of low nox emission in circulating fluidized bed decoupling combustion

博士学位论文 Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion 作者姓名: 指导教师: DO HAI SAM 许光文 (研究员，中国科学院过程工程研究所) 高士秋 (研究员，中国科学院过程工程研究所) 学位类别: 工学博士 学科专业: 化学工程 培养单位: 中国科学院过程工程研究所 2018 年 6 月 Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion A dissertation submitted to University of Chinese Academy of Sciences in partial fulfillment of the requirement for the degree of Doctor of Philosophy in Chemical Engineering By Hai-Sam Do Supervisors: Professor Guangwen Xu Professor Shiqiu Gao Institute of Process Engineering Chinese Academy of Sciences June 2018 摘 要 摘 要 循环流化床解耦燃烧（CFBDC）实现低氮氧化物（NOx）排放的技术可行性 已在处理白酒糟（DSL）的工业示范装置上得到了很好验证。低 NOx 排放被认 为是由包括焦炭，焦油和热解气（py-gas）的 DSL 热解产物在燃烧器中再燃时共 同还原 NOx 的结果。为揭示 CFBDC 系统中还原 NOx 的机理，本研究采用实验 室规模的沉降炉（DTR）反应器，模拟 CFBDC 再燃条件，研究了生物质半焦、 焦油和热解气对 NO 的还原能力，并因此概算了 CFBDC 中各热解产物组分的潜 在作用。 本论文在 500℃下热解 DSL 制备测试用半焦和焦油，py-gas 根据实验所得热 解气的组成采用钢瓶气配制。为确保 NO 被充分还原，大多数实验在反应物总质 量给料速度 0.15g / min 条件下进行。第 4 章首先研究了 NO 还原效率（ηe）随反 应物进料速率、再燃化学计量比（SR）、反应温度、停留时间和初始烟气组成的 变化。结果表明，在相同质量流速条件下，焦油较半焦和热解气更能抑制 NO 的 产生。热解气中 CO 的存在抑制了均相 NO 还原反应，导致热解气的 ηe 较低。对 于由 DSL 制备的半焦和焦油，高温和高的初始 NO、CO 浓度促进其对 NO 的还 原。 本章的主要结论是： 通过热解产物再燃烧获得最高 ηe 的适当 SR 值为 0.6-0.8。 基于上述结果，第 5 章研究了焦炭，焦油和热解气对 NO 还原的协同效应。 结果表明，NO 还原物的总质量流速一定时，焦炭/热解气混合物（二元反应物） 比其它混合物能够实现最佳的协同 NO 还原效果，且还原效率随着热解气比例的 增加而升高。而只有当焦油比例降低至 26％时，焦油/热解气或焦油/半焦混合物 才产生积极作用。此外，热解产物在还原 NO 过程中，焦炭与某些物质（如 H2， CxHy）之间存在有效的相互作用，其协同效应与反应物中 C，H 元素与进料 NO 的摩尔比密切相关（CH/NO 比）。 第 6 章进一步研究了来源于其他燃料如木屑（SD）和先锋（XF）褐煤的焦 炭和焦油的还原能力。在一定的还原物质量比率下（0.15g/min），SD 焦炭或 XF 褐煤焦由于灰分含量较低（具有催化物质），还原 NO 效率低于 DSL 焦炭，但 SD 焦油在三种焦油中实现的 ηe 最高。值得注意的是，焦油总是表现出比焦炭更 好的 NO 还原能力。以苯酚、苯、乙酸、乙酸甲酯和庚烷等作为模型焦油化合物 I 循环流化床解耦燃烧过程低 NOx 排放机理研究 还原 NO 的实验表明， 焦油中的苯酚发挥的作用显著。无论是生物质焦油还是 煤焦油，含有至少一个芳香环（如苯酚，苯）的化合物组分都是还原 NO 的主要 贡献者。 本研究的结果将对应用 CFBDC 技术处理富 N 燃料在操作运行方面具有重 要指导意义。考虑到热解产生的焦油是降低 CFBDC 中 NOx 排放的主导因素， 建议今后研究集中于焦油还原 NO 的动力学，以及焦油与其他成分的协同作用。 另外，热解温度对不同反应物还原 NO 活性的影响也值得研究。 关键词：热解，NO 还原，再燃，解耦燃烧，循环流化床，生物质，煤，低 NOx 燃烧，下降管反应器。 II Abstract Abstract The technical feasibility of low-NOx circulating fluidized-bed decoupling combustion (CFBDC) has been well proved in an industrial demonstration plant treating distilled spirit lees (DSL). The lowered NOx emission was believed to result from the combined contributions of DSL pyrolysis products including char, tar, and pyrolysis gas (py-gas) to the reduction of NOx via their reburning in the riser combustor of the CFBDC system. In order to further understand the mechanism of NOx reduction in CFBDC, this study is devoted to investigating the capabilities of biomass char, tar and py-gas for NO reduction through experiments in a lab-scale drop-tube reactor (DTR) that simulates the reburning conditions occurring in CFBDC. The work performed pyrolysis of DSL at 500 °C to produce the tested char and tar reactants while py-gas was prepared by mixing pure gases from cylinders according to the analyzed py-gas composition. In order to ensure the sufficient reduction of NO, a total mass feeding rate of reagents, which is 0.15 g/min, was adopted for most experiments. We first investigated in Chapter 4 the variations of acquired NO reduction efficiency (ηe) with major parameters including reagent feeding rate, reburning stoichiometric ratio (SR), reaction temperature, residence time, and initial flue gas composition. It was found that tar enabled the best NO reduction in comparison to char and py-gas did at the same mass feeding rate of reagent (0.15 g/min). The presence of CO in py-gas inhibited the homogeneous NO reduction reactions to cause lower ηe. For DSL-derived char and tar, their realized ηe were facilitated through by higher temperatures and higher initial NO and CO concentrations. The main conclusion of this chapter is that the suitable SR values for obtaining the highest ηe by reburning of pyrolysis products were found to be 0.6 − 0.8. Based on preceding results, the synergetic effects among char, tar and py-gas reagents on NO reduction were evaluated and discussed in Chapter 5. The comparison at given total mass flow rate of NO-reduction reagent indicated that the char/py-gas (binary reagent) enabled the best synergetic NO reduction than the others did. Its realized efficiency elevated with increasing of the py-gas proportion. The tar/py-gas or tar/char mixture caused a positive effect only when the tar proportion was necessarily lowered to about 26%. In addition, there existed obvious interactions between char and some species in py-gas (i.e., H2, CxHy) for NO reduction by pyrolysis products. The III Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion synergetic effects were closely related to the molar ratio of C and H elements in reagents over the fed NO (CH/NO ratio). The NO reduction capabilities of char and tar reagents derived from other fuels such as sawdust (SD) and Xianfeng (XF) lignite were further investigated in Chapter 6. At the specified mass flow rate of reductant, say, 0.15 g/min, the SD char or XF lignite char were less efficient than the DSL char did for reducing NO because of the lower contents of ash (containing catalytic matters) in the SD and XF lignite chars. However, the SD tar enabled the highest ηe among the three tested tars. Above all, tar as an attractive reagent always exhibits the better NO reduction than char does. Testing model tar compounds including phenol, benzene, acetic acid, methyl acetate and heptane for NO removal revealed that phenol plays an important role in enabling the good NO reduction by the SD tar. Our major understanding from testing the NO reduction by tar is that the compounds containing at least one aromatic ring (e.g. phenol, benzene) are the major contributor for reducing NO in either biomass tar or coal tar. In conclusion, the results of this study would be significant in the operation of CFBDC technology treating N-rich fuel. By considering the pyrolysis-generated tar as a dominant factor in lowering NOx emission in a CFBDC system, further studies are suggested to focus on kinetic analysis of the NO reduction by tars and also on the combined action of tar with other reagents. Additionally, the effect of pyrolysis temperature on NO reduction activity by various reagents should be investigated. Key words: pyrolysis, NO reduction, reburning, decoupling combustion, circulating fluidized bed, biomass, coal, low-NOx combustion, drop-tube reactor. IV Table of Contents Table of Contents Chapter 1  Introduction ..........................................................................1  1.1  Background .................................................................................................... 1  1.2  Objectives and Significance ........................................................................... 3  1.3  Thesis Outline ................................................................................................ 4  Chapter 2  Literature Review .................................................................7  2.1  Nitric Oxides .................................................................................................. 7  2.1.1  Sources of NOx .......................................................................................... 7  2.1.2  NOx Emission in China ............................................................................. 7  2.2  Low-NOx Emission Strategy ......................................................................... 9  2.2.1  NOx Formation During Fuel Combustion ................................................. 9  2.2.2  NOx Reduction Technologies .................................................................. 11  2.3  Decoupling Combustion (DC) for Lowering NOx Emission ...................... 14  2.3.1  Principle of Decoupling and DC Technology .......................................... 14  2.3.2  Low-NOx Emission in Grate-Based DC.................................................. 16  2.3.3  Low-NOx Emission in CFBDC ............................................................... 18  Chapter 3  Material and Methodology ................................................25  3.1  Preparation of NO-Reduction Reagents....................................................... 25  3.1.1  Feedstock Material ................................................................................... 25  3.1.2  Pyrolysis Setup and Procedure................................................................. 25  3.1.3  Characteristics of NO-Reduction Reagents ............................................. 28  3.2  Experimental Drop-Tube Reactor for NO-Reduction Evaluation ............... 30  3.2.1  Main Chamber ......................................................................................... 30  3.2.2  Heating Control System ........................................................................... 31  3.2.3  Reagent-Feeding System ......................................................................... 32  3.2.4  Flue-Gas Supplying System ..................................................................... 35  3.2.5  Sampling and Analyzing System ............................................................. 36  3.3  Experimental Procedure ............................................................................... 37  3.3.1  Procedure and Analysis ............................................................................ 37  3.3.2  Validation of Experimental Setup Conditions.......................................... 39  Chapter 4  NO Reduction by Biomass Pyrolysis Products ................45  4.1  Introduction .................................................................................................. 45  4.2  Experimental Conditions ............................................................................. 45  V Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion 4.3  Results and Discussion ................................................................................ 46  4.3.1  NO Reduction Varying with Reagent Feeding Rate ................................ 46  4.3.2  NO Reduction Varying with SR ............................................................... 49  4.3.3  NO Reduction Varying with Reaction Temperature ................................ 53  4.3.4  NO Reduction Varying with Residence Time .......................................... 54  4.3.5  NO Reduction Varying with Flue Gas Composition................................ 55  4.4  Conclusions .................................................................................................. 61  Chapter 5  Synergetic Effect Among Pyrolysis Products in Reducing NO .......................................................................63  5.1  Introduction .................................................................................................. 63  5.2  Experimental Conditions ............................................................................. 63  5.3  Results and Discussion ................................................................................ 65  5.3.1  Synergetic Effect of Binary Reagent ....................................................... 65  5.3.2  Synergetic NO Reduction Varying with Reaction Temperature .............. 70  5.3.3  Synergetic NO Reduction Varying with Residence Time ........................ 71  5.3.4  Synergetic NO Reduction Varying with Gas Species .............................. 72  5.4  Conclusion ................................................................................................... 76  Chapter 6  NO Reduction by Reagents Derived from Different Fuels. ..............................................................................................77  6.1  Introduction .................................................................................................. 77  6.2  Materials and Experimental Conditions....................................................... 77  6.2.1  Materials .................................................................................................. 77  6.2.2  Experimental Conditions ......................................................................... 79  6.3  Results and Discussion ................................................................................ 81  6.3.1  NO Reduction by Char Reagents and Effect of Ash Content .................. 81  6.3.2  NO Reduction by Tar Reagents and Model Tar Compounds ................... 88  6.4  Conclusions .................................................................................................. 98  Chapter 7  Conclusions and Recommendations .................................99  7.1  Conclusions .................................................................................................. 99  7.2  Innovation .................................................................................................. 101  7.3  Recommendations for Future Work ........................................................... 101  Nomenclatures .......................................................................................103  References ..............................................................................................105  Appendix A  Chemical Compositions of Tested Tar Reagents ...... 115  A.1 GC–MS Spectra .............................................................................................. 115  VI Table of Contents A.2 Identified Compounds of Tar .......................................................................... 116  Appendix B  Calibration Curves of Feeders for Different Reagents . ......................................................................................... 119  Acknowledgement .................................................................................121  Résumé ...................................................................................................123  VII Chapter 1 Introduction Chapter 1 Introduction 1.1 Background Since the 20th century, the world has been improving so fast with the rapid development of industries and technologies, as a result huge amounts of industrial wastes are produced. For example, distilled spirit lees from beverage industries, sawdust from the wood industries, mycelial wastes from medicine industries, sewage sludge from wastewater plant and so on have already been the major resource of biomass named industrial biomass wastes. Most of them are of similar properties with high organic matter, high nitrogen and water contents, which cause a lot of environmental problems and have very few effective utilization ways until now. Fig. 1.1 Distilled spirit lees (DSL) disposal. In term of beverage industries, China is a large spirits-producing country. Therefore, the output of solid residue such as distilled spirit lees (DSL) generated in the unique solid-state fermentation process (Fig. 1.1) is enormous all over the country. In fact, DSL amounts to 20 million tons per year (Deng and Luo, 2004) and can be considered as a good biomass resource due to its being rich in cellulose and hemicellulose. Traditionally, the DSL have sufficiently high nutrition content for being feedstuff or protein substrate of animals such as pig. With progress in the biotechnology, the digestible nutrition in the lees becomes so low that it cannot meet the requirement of animal feedstuff. Nowadays, except for apart used as the filler material for animal feedstuff or as fertilizer, the DSL is mainly landfilled or discharged to the open air 1 Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion (Deng and Luo, 2004; Zhang et al., 1997). However, the high moisture in DSL, even up to 60 wt. %, and the properties of easy putrescibility and strong acidity can cause serious environmental problems, such as smelly gas release and underground water pollution (Xu et al., 2009a). Therefore, highly reliable technologies for clean, rapid and large-scale utilization of DSL are in a great demand in the spirits industry of China, especially for large distiller factories. The nature of rich in cellulose in DSL makes it hardly treated via biological conversion technologies. The thermal conversion of the lees into the energy usable in the distiller factories, such as steam or fuel gas, is thus considered to be viable. Burning DSL to produce steam in fact not only limits the pollution as a result of DSL disposal but also offers a part of energy required by distilled spirits production (Xu et al., 2007). However, as a result of its relatively high N content (about 3 – 5 wt. % on a dry basis), direct combustion of DSL via the traditional way has to release high NOx emission, which is one of the main gas-phase pollutants released in fuel combustion, not only injures human health but also forms acid rain and photochemical smog (Winter et al., 1999; Calvert, 1997). The NOx content in the flue gas can even reach up to 550 ppm during burning this material in a laboratory fluidized bed (Zhu et al., 2015). In order to reduce NOx emission in combusting high-N biomass waste and also improve the combustion efficiency of a conventional circulating fluidized bed, the so-called circulating fluidized-bed decoupling combustion (CFBDC) technology has been investigated and developed by our Advanced Energy Technology Laboratory (AET Lab), Institute of Process Engineering (IPE), Chinese Academy of Sciences (CAS). The technology has been well proven by an industrial system treating DSL. The actual running data show that the NOx emission was lowered by about 70% comparing to the traditional CFB combustion (Han et al., 2015; Yao et al., 2011; Xu et al., 2010), making the NO content in its flue gas be 120 – 170 mg/Nm3 for the DSL containing N of about 4.0 wt.%. This kind of technologies can also be applied to many other lees and residues such as vinegar lees and Chinese herb residues generated in various light industrial processes (Yao et al., 2011). The CFBDC technology is based on the reaction decoupling concept which separates the combustion process into drying/pyrolysis of fuel and combustion of pyrolysis-generated char and volatile. Thus, the system is composed of a fluidized-bed pyrolysis reactor and a riser combustor, the pyrolysis-generated volatile consisting of non-condensable pyrolysis gas (py-gas) and condensable tar is sent to an intermediate 2 Chapter 1 Introduction position of the riser combustor to allow its co-burning with char, as conceptualized in Fig. 1.2. The co-burning of fuel pyrolysis products in such an intermediate position can be considered as a reburning way that effectively reduces the NOx formed by burning char in the bottom zone. Therefore, more fundamental studies refer to reburning chemistry are suggested to further understand the low-NOx emission mechanism in CFBDC system. This would facilitate the technology scale-up and also contribute to update the technical designs for CFBDC. Flue gas Heated HCPs + unburnt char Distilled spirit lees Py-gas & Tar Riser Combustor Air Fluidized Bed Pyrolyzer Temperature-lowered HCPs + char N2 / Air Fig. 1.2 Principle conception of circulating fluidized bed decoupling combustion (CFBDC). 1.2 Objectives and Significance The approaches of the decoupling principle for innovating combustion technologies were unquestionably effective, namely in term of lowering NOx emission. The NOx reduction mechanisms in the developed coal/biomass combustion devices have been systematically studied by AET Lab to determine better control strategies associated with the technologies involving decoupling conception. Thereby, the reduction effects of char and reducing gas on NO (as the main component of NOx in most practical flue gas) were analyzed in detail (Cai et al., 2013; Dong et al., 2010, 2009, 2007; He et al., 2006). Recently, tar species derived from the pyrolysis of DSL was found to reduce NOx significantly by the analysis in micro-fluidized bed reactor (Song et al., 2014). However, the experimental conditions in earlier investigations were actually not close enough to the reburning condition in CFBDC due to the limitations 3 Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion of batch or semi-batch reactors adopted. In addition, those studies are still far from fully understanding the interactions occurred within the practice system since the combined actions of NOx reduction in the reburning zone by different agents including char, tar and py-gas have not been previously considered. Above all, the complexity of the NO reduction reactions required that further experimental work must be carried out in order to understand some key aspects of the process. Therefore, it is highly worthwhile to deepen such studies for further understanding the mechanism of low-NOx emission in CFBDC treating not only DSL but also other fuels such as sawdust or coal. To implement this plan, a continuous drop-tube reactor (DTR) was indeed adopted to facilitate the investigations on the characteristics of NO reduction using char, tar and py-gas from pyrolysis of different fuels as reagents, these aim to (i) figure out the dominant NO reduction reactions for CFBDC, (ii) provide the optimal conditions for operating CFBDC system in term of achieving high NOx reduction, (iii) reveal the synergetic effect among char, tar and py-gas on NO reduction occurring during their reburning in CFBDC, (iv) understand the combined homogeneous–heterogeneous reaction mechanism for NO reduction, (v) understand the different NO reductions for tars, chars derived from different fuels and the contributions of their constituents to the achieved NO reduction. 1.3 Thesis Outline This thesis discusses basically on two following topics (i) reduction of NO by DSL pyrolysis products including char, tar and py-gas in both individual and combined actions, (ii) reduction of NO by reagents derived from different fuels in comparison with that by DSL-derived products. The contents are divided into seven chapters. The first chapter served as an introduction where the brief background of CFBDC are given, followed by the research objectives and approach. Chapter 2 provides a literature review about the theoretical background and current state of research essential for the discussion of experiment results. Chapter 3 introduces the materials and the main experimental techniques used in 4 Chapter 1 Introduction this study. Namely, the preparation of NO-reduction reagents from DSL, the design of experimental apparatus, the procedure and analysis of experiments were described in detail. Chapter 4 begins presenting the results of this study. The NO reduction characteristics of DSL-derived char, tar and py-gas are shown and discussed, from which the influences of reagent feeding rate, reburning stoichiometric ratio (SR), reaction temperature, residence time, initial composition of flue gas on NO reduction by each reagent are put into evidence. Chapter 5 covers the synergetic effect of reagents on NO reduction. The results of NO reduction tests using the mixtures of binary reagents among char, tar and py-gas derived from DSL are given and discussed in function of SR, temperature and residence time. Moreover, the effects of gas species in py-gas such as CO, H2, CH4 on NO reduction by char/py-gas mixture are presented. Chapter 6 examines the NO reduction by tars, chars derived from different fuels such as such as SD and XF coal. The results in this chapter are brought together with those in Chapter 4 in order to compare the capabilities of different reagents for reducing NO. The difference in NO reduction by chars is discussed based on the analysis of catalytic matter in ashes, while the contribution of some components in tars to the overall NO reduction is provided in addition to explain the reactivity of tars for NO removal. Chapter 7 briefly summarizes the key conclusions of this study and provides a few recommendations for future research directions. 5 Chapter 2 Literature Review Chapter 2 Literature Review 2.1 Nitric Oxides Nitrogen oxides (NOx), some of the main gas-phase pollutants released in fuel combustion, are a very interesting and important family of air pollutant. NOx not only injures human health but also forms acid rain and photochemical smog (Winter et al., 1999; Calvert, 1997). Therefore, a strict legislation is thus being considered or has been implemented by many countries, including China, to lower the emission of NOx. 2.1.1 Sources of NOx There are two sources of NOx emission generated by human activities such as mobile sources and stationary sources. Automobiles and other mobile sources contribute about half of the NOx that is emitted, while electric power plant boilers produce about 40% of the NOx emissions from stationary sources (United States Environmental Protection Agency, 1999). The substantial emissions are also added by such sources as industrial boilers, incinerators, gas turbines, reciprocating spark ignition and diesel engines in stationary sources, iron and steel mills, cement manufacture, glass manufacture, petroleum refineries, and nitric acid manufacture. In addition, biogenic or natural sources of nitrogen oxides including lightning, forest fires, grass fires, trees, bushes, grasses, and yeasts are also involved in the global NOx emission. These various sources produce differing amounts of NOx but almost three-quarters of the total amount of NOx emission is contributed by human activities through combustion of fossil and alternative fuels (including field burning and forest fires) (Topsoe, 1997; Bosch and Janssen, 1988). 2.1.2 NOx Emission in China China is the largest NOx emission country in Asia contributing 41% – 57% of Asian NOx emissions (Fei et al., 2016; Wang et al., 2014; Wang and Hao, 2012; Zhao et al., 2008; Ohara et al., 2007; Mauzerall et al., 2005). With the rapid growth of energy consumption, NOx emissions were estimated to more than double from 11.0 Mt in 1995 to 26.1 Mt in 2010, with an annual growth rate of 5.9%. Power plants, industry and transportation were major sources of NOx emissions, accounting for 28.4%, 34.0%, and 25.4% of the total NOx emissions in 2010, respectively (Zhao et al., 2013b). In 2014, 7 Mechanism of Low-NOx Emission in Circulating Fluidized-Bed Decoupling Combustion 2.5 million tons of NOx were emitted from industrial boilers, which accounted for 12.3% of total Chinese NOx emissions. Industrial boilers are the third largest emission source, after power plants and vehicles (Ministry of Environmental Protection of the People’s Republic of China, 2014). Based on current legislation and implementation status, defined as a business as usual (BAU) scenario according to Zhao et al. (2013b), NOx emissions in China are estimated to increase by 36% in 2030 from 2010 level. In detail, the trend in NOx emissions and that prediction for 2020 and 2030 of each province in China are listed in Table 2.1. Table 2.1 Provincial NOx emissions during 2005 – 2030 (Mt) in China (Zhao et al., 2013b). 8 Province 2005 2010 Beijing Tianjin Hebei Shanxi Inner Mongolia Liaoning Jilin Heilongjiang Shanghai Jiangsu Zhejiang Anhui Fujian Jiangxi Shandong Henan Hubei Hunan Guangdong Guangxi Hainan Chongqing Sichuan Guizhou Yunnan Tibet Shaanxi Gansu Qinghai Ningxia Xinjiang Total 0.41 0.31 1.35 0.84 0.70 0.90 0.46 0.60 0.41 1.49 1.08 0.68 0.43 0.36 1.97 1.40 0.65 0.64 1.35 0.39 0.06 0.27 0.60 0.42 0.36 0.01 0.46 0.32 0.06 0.18 0.34 19.48 0.48 0.41 1.62 1.05 1.16 1.15 0.64 0.72 0.47 1.75 1.27 0.99 0.73 0.50 2.52 1.86 0.96 0.84 1.76 0.58 0.09 0.46 0.98 0.52 0.52 0.02 0.68 0.46 0.09 0.30 0.49 26.05 Business as Usual (BAU) Scenario 2020 2030 0.47 0.46 0.46 0.49 2.11 2.30 1.35 1.50 1.52 1.70 1.40 1.56 0.68 0.78 0.88 0.97 0.59 0.65 2.07 2.22 1.54 1.63 1.21 1.40 1.02 1.16 0.62 0.74 3.01 3.13 2.16 2.45 1.09 1.24 1.04 1.21 2.16 2.40 0.72 0.84 0.12 0.14 0.52 0.61 1.10 1.27 0.69 0.81 0.63 0.75 0.03 0.03 0.86 1.02 0.59 0.70 0.10 0.12 0.40 0.46 0.56 0.63 31.69 35.35