CN101906324B - 生物质水蒸汽间接气化工艺及其设备 - Google Patents
生物质水蒸汽间接气化工艺及其设备 Download PDFInfo
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- CN101906324B CN101906324B CN2010102340866A CN201010234086A CN101906324B CN 101906324 B CN101906324 B CN 101906324B CN 2010102340866 A CN2010102340866 A CN 2010102340866A CN 201010234086 A CN201010234086 A CN 201010234086A CN 101906324 B CN101906324 B CN 101906324B
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- Industrial Gases (AREA)
Abstract
一种生物质水蒸汽间接气化工艺及其设备。该工艺利用高温过热水蒸汽作为氧化剂和能量载体,首先在温度为1200~1600℃的气化炉内使生物质燃料经过干燥、挥发份析出、裂解和气化反应,生成不含焦油的粗合成气;然后在喷淋塔内对粗合成气进行激冷淬火处理,使其温度骤降至650~800℃,获得不含熔渣和碱金属氧化物的初合成气;最后对初合成气依次进行冷却、除尘、脱酸和干燥处理,即可获得高品质的净合成气。其设备主要由储水箱、输水泵、热交换器、等离子炬加热器、气化炉、喷淋塔等部件组成。本发明工艺易于控制、能耗和投资低廉、冷煤气效率高,所产生合成气热值大、不含焦油和碱金属化合物。既适合于生物质气化联合循环发电,也适合于制取生物质液体燃料。
Description
技术领域
本发明涉及将可燃物料转变成清洁高效合成气的技术,具体地指一种生物质水蒸汽间接气化工艺及其设备。
背景技术
可燃物料气化技术在二十世纪末得到了快速发展,特别是对燃煤进行气化的技术已经相当成熟,科研人员已成功地开发出了对煤种适用性广、气化效率高、产生污染少的煤气化工艺。而对树枝、秸秆、稻草或其他农林废弃物等生物质进行气化的技术则是本世纪出现的一种综合利用能源的新技术,已有的生物质气化技术主要包括固定床气化工艺、流化床气化工艺、两段式制气工艺等等,这些都属于直接气化工艺。直接气化工艺最主要的特点是利用部分生物质燃烧放出的热量为气化反应提供能源,气化反应所采用的氧化剂一般是空气、富氧空气、或富氧空气与水蒸汽的组合中的一种。近期的研究和实验表明:上述生物质直接气化工艺存在如下几方面的缺陷:
、生物质燃料的成份和热值极不稳定、着火点低、着火反应快,容易发生爆燃现象,在气化炉局部区域形成超温结焦结垢,气化炉的运行温度极难控制。
二、当以空气作为氧化剂时,由于空气中存在大量不发生反应的N2成份,会导致合成气中的N2含量偏高、有效气体(CO+H2)含量偏低、H2/CO比例下降,合成气的热值偏低且不稳定,一般只能维持在5000KJ/Nm3以下,难以满足后续的工业利用。
三、当以富氧空气作为氧化剂时,虽然可以减少合成气中的N2含量,但需要附设体积庞大且能耗极高的空气分离装置,这样将大幅增加整个气化工艺的成本。
四、当以富氧空气与水蒸汽的组合作为氧化剂时,虽然可以减少合成气中的N2含量、增加合成气中的H2含量,但水蒸汽作为反应介质仍需要消耗大量的热能,与分离空气的能耗累积,同样会大幅增加整个气化工艺的投资。
五、需要自燃约15~20%的生物质来提供气化反应的能量,而燃烧产生大量的CO2,从而降低合成气中有效气体(CO+H2)的含量。并且,高温合成气连同混杂于其中的空气将带走大量的显热,这样热能转化成化学能的比例将大幅下降,导致整个气化工艺的冷煤气效率较低,一般情况在70%以下,最好状况也不会超过80%。
六、气化炉的运行温度大多设计为800~1200℃,而在该温度区域进行气化反应的生物质燃料将产生大量难以清除的焦油,过多的焦油在设备和管道中累积和粘结,可造成管道堵塞和设备污染。
七、生物质燃料气化反应所产生的灰份中含有大量的K、Na等碱金属氧化物,一般占灰份重量的20~40%,而这些碱金属氧化物在温度高于800℃时会气化混杂于所产生的合成气中,不仅影响合成气的品质,而且与焦油一起粘附在设备和管道中,对设备和管道腐蚀严重。
鉴于上述生物质直接气化工艺所存在的若干致命缺陷,目前还难以将其应用于实际生产中。如何使生物质燃料的气化工艺从研究试验阶段转化为实际商业利用,是本领域科研人员一直在努力攻克的难题。
发明内容
本发明的目的就是要提供一种工艺易于控制、能耗和投资低廉、冷煤气效率高、所产生合成气热值大、且能根除焦油和碱金属化合物的生物质水蒸汽间接气化工艺及其设备。
为实现上述目的,本发明所设计的生物质水蒸汽间接气化工艺,是利用高温过热水蒸汽作为氧化剂和能量载体、在气化炉内将生物质燃料转变成粗合成气、在喷淋塔内对粗合成气进行淬火处理、最终生成净合成气的过程。该工艺包括如下步骤:
1)将破碎好的生物质燃料投入到气化炉内,同时向气化炉内喷入高温过热水蒸汽,高温过热水蒸汽的热量应能始终保持气化炉内的运行温度为1200~1600℃,使生物质燃料与高温过热水蒸汽充分接触,依次经过干燥、挥发份析出、裂解和气化反应,生成粗合成气和灰渣。由于气化炉内的运行温度高于焦油类物质的形成温度,因此生物质燃料在中间裂解过程中所产生的焦炭和焦油将被完全气化,所生成的粗合成气中基本上不含焦油组份。所产生的灰渣则由气化炉的排渣口输出,经过冷却降温或回收余热后送入灰渣库,可进行综合利用。
2)将所生成的粗合成气引入到喷淋塔内,通过喷淋水对其进行激冷淬火处理,使其温度陡降至650~800℃。由于粗合成气淬火后的温度低于K、Na等碱金属氧化物的升华温度,且碱金属氧化物易溶于水,故在此温度下粗合成气中含有的熔渣和微量焦油被喷淋水凝结分离、碱金属氧化物和部分酸性气体被喷淋水溶解带走,从而获得不含或仅含微量碱金属氧化物的初合成气。
3)对所获得的初合成气依次进行冷却降温、清除粉尘、脱除酸性气体和脱水干燥处理。冷却降温一方面是制取合成气工艺上的需要,另一方面可以回收大量显热进行综合利用。清除粉尘可以将初合成气中携带的粉尘捕获出来,最好使初合成气含尘浓度小于50mg/Nm3。脱除酸性气体可以除去初合成气中的H2S、COS、HCL、NH3、HCN等有害气体。净化后的初合成气再经过脱水干燥处理,即可获得净合成气,供下游的工业应用。
上述步骤1)中,生物质燃料的粒径优选控制在50mm×50mm以下,生物质燃料中水份的重量含量优选小于40%。控制尺寸和水份含量均衡,有利于生物质燃料在下降过程中与高温过热水蒸汽充分接触,平稳实现干燥、挥发份析出、裂解和气化反应,且气化炉的运行温度易于控制。
上述步骤1)中,最好在气化炉的进料口处设置氮气保护气氛,以防止气化炉内的粗合成气外泄引发火灾和爆炸的危险。
上述步骤1)中,优选气化炉内的运行温度为1200~1400℃、运行压力为105~109Kpa。由于气化炉的运行温度适中,生物质燃料在与高温过热水蒸汽充分接触的过程中既能够完全气化、获得不含焦油的粗合成气,又能够尽量降低热能消耗、大幅提高气化炉运行的性价比。同时,气化炉在常压状态运行,无需另设压力设备,投资成本低廉。
上述步骤1)中,优选高温过热水蒸汽的喷入速度为35~50m/s、粗合成气在气化炉内的停留时间为15~20s、粗合成气的引出速度为15~20m/s。高温过热水蒸汽较高的喷入速度可以加大其与生物质燃料的扰动、接触、混合,而粗合成气较低的引出速度可防止其携带灰渣在气化炉出口和烟道粘结累积。
上述步骤2)中,最好通过喷淋水冷却将粗合成气的温度陡降至750~800℃,该温度正好处于碱金属氧化物升华温度的边界之下。这样,既可以确保粗合成气中携带的粉尘、熔渣、微量焦油和碱金属氧化物在喷淋水的冲刷下分离出来、并随喷淋水排走,有可以尽量保留所获得初合成气中的热能,以利于在后续的冷却降温工艺中回收利用。
上述步骤3)中,先将所生成的初合成气冷却降温至260~320℃,再进行净化处理。由于从喷淋塔引出的初合成气温度仍然高达750~800℃,冷却降温既有利于后续的除尘、脱酸和干燥处理,又可以利用其间约430~540℃的温差,充分回收初合成气中的显热,实现余热综合利用。
为实现上述工艺而设计的生物质水蒸汽间接气化设备,包括通过各种管道相连的储水箱、输水泵、热交换器、等离子炬加热器、气化炉和喷淋塔等部件。其中:
所述储水箱通过输水泵与热交换器的给水输入端相连,所述热交换器的蒸汽输出端与等离子炬加热器的进汽口相连,所述等离子炬加热器的排汽口与气化炉的水蒸汽喷嘴相连。
所述气化炉的排渣口与冷渣器的进渣口相连,所述气化炉的出气口与喷淋塔的进气口相连,所述喷淋塔的出气口与热交换器的气体输入端相连,所述热交换器的气体输出端依次与除尘器、除酸塔和干燥器串联连接。
由于等离子炬加热器具有可超高温加热、传热传质快、热效率高、热功率可调等特点,用其加热储水箱中的水时,能够高效、连续、稳定地输出符合工艺要求的高温过热水蒸汽,高温过热水蒸汽既作为氧化剂又作为能量载体,可确保气化炉始终维持稳定可靠的运行。而热交换器的设置可以有效回收初合成气所携带的大量显热,这些显热可将储水箱中的水预热成饱和蒸汽,再送入等离子炬加热器处理,这样可以降低等离子炬加热器的能耗,同时实现热能的综合利用。
进一步地,所述气化炉的进料口处连接有氮气保护装置。在从气化的进料口投放生物质燃料时,也向该进料口输送氮气,所形成的氮气密封层既可防止气化炉内的粗合成气外泄,又可阻止外界空气进入气化炉,从而杜绝火灾和爆炸的危险,并确保粗合成气的品质。
更进一步地,所述气化炉的水蒸汽喷嘴沿炉体的高度方向布置有3~4层,每层沿圆周方向均匀切向分布。这样,高温过热水蒸汽分多层喷入,能够始终维持气化炉内沿高度方向的温度场稳定、均匀,确保高温过热水蒸汽与生物质燃料充分接触。
本发明在仔细研究和分析生物质中水份、灰份、挥发份和灰熔点等固有特性的基础上,结合气化炉的运行特点,摒弃传统氧化剂空气或富氧空气,转而利用高温过热水蒸汽在气化炉中对生物质燃料连续进行干燥、挥发份析出、裂解和气化处理,再利用喷淋水对所生成的粗合成气进行激冷淬火处理,其优点主要体现在如下几方面:
其一,采用高温过热水蒸汽间接气化生物质燃料,高温过热水蒸汽既是氧化介质又是能量载体,这样不需要空气或富氧空气,工艺中省略了高能耗的空气分离装置,大幅降低了整个工艺的能耗及工程总投资。
其二,生物质燃料在连续干燥、挥发份析出、裂解和气化的流程中无自身的燃烧反应,有效解决了传统气化过程中炉内燃料爆燃而产生局部结焦的难题,气化炉的运行易于掌控。且因为无需空气或富氧空气参入反应,所得合成气中H2/CO的比例高,有效气体(CO+H2)的含量高,可达到85%以上,从而可大幅提高合成气的热值,拓宽合成气的用途。
其三,生物质从原料转变成初合成气主要在气化炉和喷淋塔两级装置中连续完成。由于高温过热水蒸汽始终维持气化炉内的运行温度在焦油的气化温度之上,可将生物质燃料裂解产生的焦油全部转化为粗合成气,碳转化率极高。由于粗合成气经过喷淋塔水冷淬火后温度骤降,不仅可使其中夹杂的熔渣冷却颗粒化,而且可使其中携带的碱金属氧化物溶于喷淋水中,所获得的初合成气不含对设备、管道沾污和腐蚀的杂质。并且,由于其流程短暂、结构简单,易于实现合成气的大型化批量生产。
其四,由等离子炬加热器在气化炉外部产生的高温过热水蒸汽提供气化所需要的全部能量,生物质燃料的热能可全部转化为合成气的化学能,其冷煤气效率可比传统气化工艺提高8%左右,达到88%以上。
其五,等离子炬加热器的热效率高、输入功率可调,当生物质燃料的成份发生变化时,通过调整等离子炬加热器的功率,即可方便地调节高温过热水蒸汽的温度区域,从而维持气化炉运行稳定,确保初合成气的产量和品质稳定。
试验表明,本发明的工艺及设备能够有效气化各种生物质燃料,适合于生物质气化联合循环发电和制取生物质液体燃料等工业应用。
附图说明
附图为一种生物质水蒸汽间接气化设备的连接结构示意图。
具体实施方式
以下结合附图和具体实施例对本发明的设备和工艺作进一步的详细描述:
图中所示的生物质水蒸汽间接气化设备,主要包括用于生物质输送的皮带传送机1、中间料斗2和螺旋给料机3,用于使生物质转变成粗合成气的气化炉6,用于对粗合成气进行淬火处理的喷淋塔11,用于给气化炉6提供高温过热水蒸汽的等离子炬加热器5,用于给等离子炬加热器5提供水源的储水箱10和输水泵9,用于热能综合利用的热交换器12,以及用于合成气后续净化处理的除尘器13、除酸塔14和干燥器15。
皮带传送机1的输出端置于中间料斗2的上方进口处,中间料斗2的下方出口与螺旋给料机3的原料进口相连,螺旋给料机3的原料出口与气化炉6的进料口相连。
气化炉6是将生物质燃料转变为合成气的关键设备,其采用空气或水冷夹套式常压绝热壳体结构,内衬耐火耐蚀保温材料,具有良好的高温绝热性能。气化炉6的进料口布置在其上部或顶部,按照容量大小可设置二至四个,以确保生物质燃料能够均匀投入,维持炉内烟气流场的相对稳定。气化炉6的进料口处还连接有氮气保护装置4,所形成的氮气密封层可有效阻隔粗合成气和外界空气接触。气化炉6的水蒸汽喷嘴设置在其炉体上,且沿炉体的高度方向布置有3~4层,每层沿圆周方向均匀切向分布。这样,喷入炉体内的高温过热水蒸汽流场均匀、稳定,且不留死角,可确保其与物料生物质燃料充分接触和混合。气化炉6的排渣口采用液态排渣形式,布置在其底部,按照容量大小可设置一至二个,这些排渣口与冷渣器7的进渣口相连,用以将液态灰渣冷却至固态。气化炉6的出气口可以设置在其上部,也可以设置在其下部,通过管道与喷淋塔11的进气口相连。
喷淋塔11是对气化炉6所产生粗合成气进行淬火除渣处理的关键设备,其采用循环冷却水直接冲刷粗合成气,用于分离粗合成气中的熔渣和碱金属氧化物等杂质。喷淋塔11的出气口与热交换器12的气体输入端相连,热交换器12的气体输出端则依次与除尘器13、除酸塔14和干燥器15串联,干燥器15的输出端与储气柜16相连,用以储存净合成气。
喷入气化炉6中的高温过热水蒸汽是由储水箱10中的软水或除盐水加热转变而成的。储水箱10的输出端通过输水泵9与热交换器12的给水输入端相连。热交换器12通常选用废锅,热交换器12的蒸汽输出端与等离子炬加热器5的进汽口相连,等离子炬加热器8的排汽口通过管道与气化炉6的水蒸汽喷嘴相连。
本设备还附设有灰渣库8,可通过人工或机械的方式将冷渣器7所冷却的灰渣、喷淋塔11所冲刷下来的沉渣送至灰渣库8储存。
上述生物质水蒸汽间接气化设备在实际运行时的工艺过程概括如下:
A)将破碎好的生物质燃料经由皮带传送机1、中间料斗2和螺旋给料机3连续输送到气化炉6内,同时通过氮气保护装置4向气化炉6的进料口处输入氮气。对于灰秸秆类(树枝、树根)生物质燃料而言,控制其粒径在50mm×50mm以下、含水量小于40%。对于黄秸秆类(稻草、麦秆、茅草、玉米秆等)生物质燃料而言,其粒径要求可适当放宽。
B)储水箱10中的除盐水由输水泵9送入热交换器12的给水输入端,与从热交换器12的气体输入端进来的粗合成气进行热交换,除盐水吸收粗合成气的显热,生产0.4~0.6Mpa的饱和蒸汽,该饱和蒸汽由热交换器12的蒸汽输出端输送到等离子炬加热器5中,被加热成高温过热水蒸汽。
C)等离子炬加热器5所产生的1200~1600℃的高温过热水蒸汽从气化炉6的水蒸汽喷嘴进入其内,保持气化炉6内的运行温度为1200~1400℃、运行压力为105~109Kpa、高温过热水蒸汽的喷入速度为35~50m/s,使生物质燃料在下降的过程中与高温过热水蒸汽充分接触,经过干燥、挥发份析出、裂解和气化反应,生成粗合成气和液态灰渣,且控制粗合成气在气化炉6内的停留时间为15~20s、粗合成气的引出速度为15~20m/s。
D)气化炉6所产生的温度为1200~1400℃的液态灰渣通过其排渣口进入冷渣器7,经热能回收后降温到150℃以下,送入灰渣库8综合利用。气化炉6所产生的温度为1200~1400℃的粗合成气则通过管道输入喷淋塔11内,在冷却水的直接喷淋冲刷下,粗合成气的温度在短期内骤降至750~800℃,其中的高温熔渣被冷却颗粒化,其中的碱金属氧化物和部分酸性气体被溶解于冷却水中,并随冷却水一起排出喷淋塔11外,从而获得初合成气。喷淋塔11中的冷却水经过沉淀和过滤可循环使用,收集的沉渣则送入灰渣库8。
E)从喷淋塔11输出的不含熔渣的初合成气进入热交换器12的气体输入端,可以有效防止热交换器12结渣、积灰和腐蚀。此时初合成气仍然具有750~800℃的高温,被除盐水回收显热后,降温至260~320℃,从热交换器12的气体输出端进入除尘器13,初合成气中携带的粉尘被除尘器13捕获,除尘器13出口处初合成气的含尘浓度小于50mg/Nm3。
F)经过除尘处理的初合成气进入除酸塔14,在除酸塔14中除去初合成气中的H2S、COS、HCL、NH3、HCN等有害气体。
G)经过除酸处理的初合成气再进入干燥器15,除去其中的水份,即可获得净合成气,净合成气通过管道输送至储气柜16中保存,供下游的工业应用。
经过多次试验和数据检测,本发明所制取的净合成气的主要成份及特性如表1所示。由表1可见,本发明所制取净合成气的CO+H2含量最高可达85%,H2/CO的比值大于1,合成气的热值(LHV)为12.5~13.4MJ/Nm3,冷煤气效率在88%左右,具有良好的商业前景,非常适于生物质气化联合循环发电和制取生物质液体燃料等工业应用。
表1:
项目 | 名称 | 单位 | 数值 |
1 | CO | %(vol) | 25~35 |
2 | H2 | %(vol) | 40~50 |
3 | N2+Ar | %(vol) | 1.6~1.8 |
4 | CO2 | %(vol) | 15~20 |
5 | CH2 | %(vol) | 5~6 |
6 | CnHm | %(vol) | <2 |
7 | 合成气热值(LHV) | MJ/Nm3 | 12.5~13.4 |
8 | 冷煤气效率 | % | ~88.1 |
Claims (9)
1.一种生物质水蒸汽间接气化工艺,它是利用高温过热水蒸汽作为氧化剂和能量载体、在气化炉内将生物质燃料转变成粗合成气、在喷淋塔内对粗合成气进行淬火处理、最终生成净合成气的过程,其特征在于:该工艺包括如下步骤:
1)将破碎好的生物质燃料投入到气化炉内,同时向气化炉内喷入由等离子炬加热器直接输出的高温过热水蒸汽,保持气化炉内的运行温度为1200~1600℃,使生物质燃料与高温过热水蒸汽充分接触,依次经过干燥、挥发份析出、裂解和气化反应,生成粗合成气和灰渣;其中,高温过热水蒸汽的喷入速度为35~50m/s、粗合成气在气化炉内的停留时间为15~20s、粗合成气的引出速度为15~20m/s;
2)将所生成的粗合成气引入到喷淋塔内,通过喷淋水对其进行激冷淬火处理,使其温度陡降至650~800℃,在此温度下粗合成气中含有的熔渣和微量焦油被喷淋水凝结分离、碱金属氧化物和部分酸性气体被喷淋水溶解带走,从而获得初合成气;
3)对所获得的初合成气依次进行冷却降温、清除粉尘、脱除酸性气体和脱水干燥处理,即可获得净合成气。
2.根据权利要求1所述的生物质水蒸汽间接气化工艺,其特征在于:所述步骤1)中,生物质燃料的粒径控制在50mm×50mm以下,生物质燃料中水份的重量含量小于40%。
3.根据权利要求1或2所述的生物质水蒸汽间接气化工艺,其特征在于:所述步骤1)中,气化炉的进料口处设有氮气保护气氛。
4.根据权利要求1或2所述的生物质水蒸汽间接气化工艺,其特征在于:所述步骤1)中,保持气化炉内的运行温度为1200~1400℃、运行压力为105~109Kpa。
5.根据权利要求1或2所述的生物质水蒸汽间接气化工艺,其特征在于:所述步骤2)中,通过喷淋水冷却将粗合成气的温度陡降至750~800℃。
6.根据权利要求1或2所述的生物质水蒸汽间接气化工艺,其特征在于:所述步骤3)中,将所生成的初合成气冷却降温至260~320℃。
7.一种为实现权利要求1所述工艺而设计的生物质水蒸汽间接气化设备,包括储水箱(10)、输水泵(9)、热交换器(12)、等离子炬加热器(5)、气化炉(6)和喷淋塔(11),其特征在于:
所述储水箱(10)通过输水泵(9)与热交换器(12)的给水输入端相连,所述热交换器(12)的蒸汽输出端与等离子炬加热器(5)的进汽口相连,所述等离子炬加热器(5)的排汽口与气化炉(6)的水蒸汽喷嘴相连;
所述气化炉(6)的排渣口与冷渣器(7)的进渣口相连,所述气化炉(6)的出气口与喷淋塔(11)的进气口相连,所述喷淋塔(11)的出气口与热交换器(12)的气体输入端相连,所述热交换器(12)的气体输出端依次与除尘器(13)、除酸塔(14)和干燥器(15)串联连接。
8.根据权利要求7所述的生物质水蒸汽间接气化设备,其特征在于:所述气化炉(6)的进料口处连接有氮气保护装置(4)。
9.根据权利要求7或8所述的生物质水蒸汽间接气化设备,其特征在于:所述气化炉(6)的水蒸汽喷嘴沿炉体的高度方向布置有3~4层,每层沿圆周方向均匀切向分布。
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KR20130048778A (ko) | 2013-05-10 |
US20160145514A1 (en) | 2016-05-26 |
MX2013000838A (es) | 2013-06-28 |
EP2597136A1 (en) | 2013-05-29 |
US20130125463A1 (en) | 2013-05-23 |
WO2012010051A1 (zh) | 2012-01-26 |
US9822319B2 (en) | 2017-11-21 |
CA2805966A1 (en) | 2012-01-26 |
AU2011282340B2 (en) | 2014-09-25 |
TR201300597T1 (tr) | 2013-10-21 |
JP5627777B2 (ja) | 2014-11-19 |
CA2805966C (en) | 2019-01-15 |
JP2013531121A (ja) | 2013-08-01 |
CN101906324A (zh) | 2010-12-08 |
RU2013107371A (ru) | 2014-08-27 |
SG188946A1 (en) | 2013-05-31 |
RU2528848C1 (ru) | 2014-09-20 |
AP3767A (en) | 2016-07-31 |
EP2597136B1 (en) | 2018-10-24 |
US9290707B2 (en) | 2016-03-22 |
KR101472855B1 (ko) | 2014-12-15 |
AP2013006726A0 (en) | 2013-02-28 |
EP2597136A4 (en) | 2014-01-08 |
MY161951A (en) | 2017-05-15 |
AU2011282340A1 (en) | 2013-02-28 |
BR112013001318B1 (pt) | 2018-12-04 |
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