CN116391015A - 将固体废物转化为合成气的co变换单元 - Google Patents
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Abstract
作为设备(1)的一部分用于将固体废物转化为包含氢气的产物气流的CO变换单元(500)允许节能地使用低温热回收单元(524)中的低温热能来加热设备(1)中使用的工艺水流。
Description
本发明的主题是一种使用CO变换单元和相应的设备将固体废物转化为合成气的方法。
城市固体废物(MSW)在世界各地产生,必须加以处理。在西半球,城市固体废物要么被填埋,要么被焚烧。焚烧的重点是最大限度地利用城市固体废物的能量含量,而不是像在化学回收中那样在分子尺度上回收或再利用城市固体废物的内容物。焚烧会产生有关向大气中排放污染物的问题,这导致—取决于国家或甚至地方立法—需要做出重大的技术努力以满足国家/地方立法规定的限制。此外,通过焚烧产生的产物,例如飞灰、底灰、石膏和重金属和/或含二噁英的活性煤,对其进一步使用和/或加工带来了进一步的挑战。此外,废物转化为动力的效率,即转为热能的热值量很低,通常在20至25%的范围内。
当需要化学回收时,产量、即可用化学物质的最终结果往往需要改进和/或能量效率不合适。通常,例如通过热解等产生包含一氧化碳和氢气的气体。为了增加产物流中氢气的量,可使用CO变换反应,例如从US 2009/0077892 A1中已知。为了优化氢气输出,需要大量过量的水蒸汽供应,导致CO变换反应的产物气体中含有大量的水。当这种产物气体被冷却时,这会导致大量的冷凝,因此,在产物气体被冷却到环境温度时,在冷却系统中产生大量的低水平热量。这种能量的大部分通常被丢弃,导致低的能量效率。因此,本发明的目的是克服现有技术在这方面的缺点。
该目的通过独立权利要求的特征来解决。从属权利要求涉及本发明的优选实施方式。
本发明的提高固体回收燃料(SRF)颗粒焙烧的产物气流中氢含量的方法,所述固体回收燃料颗粒被焙烧成烧焦的颗粒,同时产生焙烧气体,所述焙烧气体被转化为包含氢气和一氧化碳的焙烧合成气,其中将包含所述焙烧合成气的合成气流提供至CO变换单元,使至少一部分一氧化碳与水蒸汽反应成二氧化碳和氢气,产生变换合成气,其中将变换合成气提供至所述CO变换单元下游的低温热回收单元,在所述低温热回收单元中,所述变换合成气被引导通过至少两个热交换器,其中所述变换合成气与至少两股水流进行热交换以加热所述至少两股水流,所述至少两股水流在产物气流的生产过程中作为工艺水在相应的热交换器的下游使用。
术语合成气在本文中被理解为包含氢气、一氧化碳和/或二氧化碳的气体。固体回收燃料颗粒由包含城市固体废物的固体废物产生。术语焙烧被理解为将固体回收燃料颗粒亚化学计量氧化以产生包含氢气和一氧化碳的粗合成气。所得到的烧焦的颗粒优选在气化单元中气化,产生合成气。将包含氢气和一氧化碳的焙烧合成气提供至CO变换单元,优选与气化过程中产生的合成气组合,该焙烧合成气例如由固体回收燃料颗粒焙烧过程中产生的焙烧气体通过热裂解产生。CO变换单元优选为包括高温CO变换单元和低温CO变换单元的两级CO变换单元,用于支持一氧化碳(CO)变换反应,其中一氧化碳和水蒸汽反应成二氧化碳和氢气。
在CO变换单元的下游,所得到的变换合成气具有高于环境温度的温度,这是通过调节CO变换单元中的化学平衡所需要的。例如,在两级CO变换单元中,合成气在约270℃的温度下进入高温CO变换反应器并在约240℃的温度下离开低温CO变换反应器。因此,变换合成气在能够被储存和/或处理(即用作原材料和/或能量储存介质)或提供至气体净化单元之前必须被冷却,在该气体净化单元中氢气与作为吹扫气体吹扫的变换合成气的其余部分分离。在变换合成气的冷却过程中,一旦温度低于露点,仍存在于变换合成气中的水蒸汽就会冷凝。然后,大量的热能以冷凝能的形式释放出来。
根据本发明,变换合成气在进入低温热回收单元之前的热能含量不会被例如空气或水冷却器丢弃到环境中,而是用于加热用于生产产物气体的至少两股工艺水流。该至少两股产物水流优选处于液态和/或气态,即液态水和/或水蒸汽。
相应的产物水流例如是用于在进入CO变换单元之前增加焙烧或其他合成气的蒸汽含量的工艺水流。替代地或累积地,在气化单元中对烧焦的颗粒进行气化期间使用工艺水流,该气化单元优选对烧焦的颗粒进行气流床气化。替代地或累积地,加热用于产生高压蒸汽的锅炉进料水。优选地,以牺牲低压水蒸汽的产生为代价使高压蒸汽的产生最大化。术语高压蒸汽在本文中被理解为包括80巴至140巴的压力,而低压蒸汽在本文中被理解为包括约3巴至12巴的压力。本文中的术语中压被理解为包括约18巴至43巴的压力。
根据优选的实施方式,将变换合成气提供至气体净化单元以产生富含氢气、优选具有99.5体积%以上的氢气含量的产物气流,同时产生吹扫气体,
其中吹扫气体和焙烧合成气均被压缩并且共同地被引入饱和塔以提高CO变换单元上游的合成气流中的水含量。
这允许容易地调节提供至CO变换单元的合成气中的水含量。通过将吹扫气体与焙烧合成气混合,确保不会释放可能存在于吹扫气体中的一氧化碳和/或氢气。
根据一个实施方式,将由烧焦的颗粒气化产生的第一合成气流提供至高压洗涤单元以提高净化的合成气流中的水含量。
高压洗涤单元的使用一方面允许减少第一合成气流中的污染物如长链碳氢化合物,另一方面允许将水分引入净化的合成气流中,从而允许精确地调节进入CO变换单元的气流的水含量。
根据一个实施方式,变换合成气在低温热回收单元中通过与以下至少一种水流热接触而被冷却:
a)用于对进入CO变换单元的合成气流进行加湿的工艺水流;
b)用于使烧焦的颗粒气化、尤其是用于淬火的进料水;以及
c)用于产生高压蒸汽的锅炉水。
特别是,如果步骤c)以及步骤a)和b)中的至少一个也被实现,则该过程被控制成使得优先产生高压蒸汽,以提高由固体回收燃料颗粒生产包含氢气的产物气流的整个过程的能量产率。优选地,每股水流通过至少一个热交换器,该热交换器被布置成使得变换合成气的热能含量得到最有效的利用。
根据一个实施方式,在低温热回收单元的热交换器中,工艺水的压力高于变换合成气的压力。这确保了在相应的热交换器中发生泄漏的情况下没有合成气渗透到相应的水流中。
根据本发明的另一个方面,提出了一种将作为固体回收燃料颗粒提供的固体废物转化为富含氢气的产物气流的设备,其包括:
焙烧单元,其中所述固体回收燃料颗粒可进料,由此可产生焙烧气体和烧焦的颗粒;
焙烧气体加工单元,其中所述焙烧气体被转化为焙烧合成气;
CO变换单元,其在所述焙烧单元的下游,可提供有至少包含所述焙烧合成气的合并的合成气流,并且其中可产生变换合成气;以及
低温热回收单元,其在所述CO变换单元的下游,可提供有变换合成气,所述低温热回收单元包括至少两个热交换器,每个热交换器可提供有变换合成气和工艺水流以提高工艺水流的温度。
这允许有效地使用变换合成气中的低温热来加热在由固体回收燃料颗粒生产产物气流中使用的工艺水流。本发明的设备的部件优选适合并旨在进行本发明的方法。
根据一个实施方式,低温热回收单元包括以下热交换器中的至少两个:
a)第二热交换器,其中水、特别是在气化单元中使用的水可由变换合成气加热;
b)第三热交换器,其中用于产生高压蒸汽的水可由变换合成气加热;
c)第四热交换器,其中用于饱和塔的水可由变换合成气加热,该饱和塔用于调节CO变换单元上游的至少焙烧合成气的水含量;
d)第五热交换器,其中用于产生高压蒸汽的水可由变换合成气加热;以及
e)第六热交换器,其中水、优选在气化单元中使用的水可由变换合成气加热。
第二至第六热交换器中的两个或多个热交换器按照其表示顺序布置,其中变换合成气的温度水平降低。例如,进入第一热交换器的变换合成气的温度高于进入第三热交换器等的变换合成气的温度。这允许在冷却变换合成气的同时有效地利用变换合成气的热能。
根据一个实施方式,该设备还包括饱和塔,其中至少焙烧合成气的水含量是可调节的。饱和塔优选是通常的湿式洗涤单元,其中水被提供在塔的顶部并从塔的贮槽(sump)中提取,同时相应的气流逆着水的流动方向流动。优选地,该设备包括低热回收单元下游的气体净化单元,其中氢气通过压力开关吸附单元分离,产生吹扫气体,而吹扫气体与焙烧合成气一起提供至饱和塔。
应当注意,权利要求中指定的各个特征可以以任何期望的技术上合理的方式彼此组合,并且形成本发明的其他实施方式。说明书、特别是与附图一起,进一步解释了本发明,并具体说明了本发明的优选实施方式。现在将参照附图更详细地解释本发明的特别优选的变型和技术领域。应当注意,附图中所示的示例性实施方式并不旨在限制本发明。附图是示意性的并且可能未按比例绘制。附图显示:
图1是将固体废物转化为包含氢气的气体的设备,其包括一氧化碳变换单元;并且
图2是一氧化碳变换单元。
图1示意性地显示了将固体废物转化为包含氢气的气体的设备1,其包括一氧化碳(CO)变换单元500。在CO变换单元500中,发生一氧化碳(CO)变换反应,其中一氧化碳(CO)与水(H2O)反应形成二氧化碳(CO2)和氢气(H2):
该反应处于化学平衡,其可以在反应物(educts)或产物的方向上以通常的方式受到影响,例如通过使用相应的温度以及特定催化剂的使用和浓度。由于反应是吸热的,因此水通常以水蒸汽的形式提供。为了将化学平衡转移到产物侧以增加氢气的产生,已经发现蒸汽与一氧化碳的摩尔比为约2.3至2.7、特别是约2.5是有利的。蒸汽优选在高于发生变换反应的压力(优选约40巴)的压力下提供。如果使用2.5的蒸汽与一氧化碳的摩尔比,则反应器中每摩尔二氧化碳残留1.5摩尔蒸汽。这导致CO变换反应的产物气体中含有大量的水。当这种产物气体被冷却时,这会导致大量的冷凝,因此,在产物气体被冷却到环境温度时,在冷却系统中产生大量的低水平热量。这种能量的大部分通常被丢弃,导致低的能量效率。
CO变换单元500是用于将固体废物转化为包含氢气的气体、特别是转化为包含氢气和氢气的合成气的设备1的一部分。在造粒设备100中,由固体废物如城市固体废物103(优选具有额外添加的生物质)制备固体回收燃料颗粒之后,将相应的固体回收燃料颗粒117输送至设备1并提供至焙烧单元200,在焙烧单元200中,在250℃至300℃的温度下对颗粒进行焙烧,即亚化学计量氧化。术语焙烧被理解为在250℃至320℃的温度下对固体回收燃料颗粒进行热化学处理。其在大气压下进行且不添加额外的氧气,例如不提供空气。在焙烧过程中,包含在固体回收燃料颗粒中的水与包含在固体回收燃料颗粒中的挥发物一样都会蒸发。包含在固体回收燃料颗粒中的生物聚合物在挥发物的释放下部分分解。焙烧过程的产物是烧焦的颗粒和焙烧气体。颗粒的焙烧导致烧焦的颗粒201,其在气化单元300中气化。焙烧的另一产物是焙烧气体202,其被提供至焙烧气体加工单元400。焙烧气体加工单元400的产物是焙烧合成气401,而气化单元300的产物是合成气301。合成气301和焙烧合成气401均包含水蒸汽、一氧化碳和氢气。将两种合成气301,401引入CO变换单元500,其将在下面的图2中详细描述。将在CO变换单元500中产生的变换合成气501转移到气体净化单元600,该气体净化单元600将氢气601与吹扫气体602分离。造粒设备100优选位于场外,即位于与用于将固体废物转化为包含氢气的气体的设备1不同的位置。
图2显示了CO变换单元500。将由气化单元300产生的第一合成气流301引入高压洗涤单元502。高压洗涤单元502是常规的湿式洗涤单元,其中例如从合成气301中去除高级烃。高压洗涤单元502供给有进料水503,该进料水503是来自稍后将描述的低温热回收的冷凝水508。收集在高压洗涤单元502的贮槽504中的水505通过输送装置506输送到排水导管507。不需要作为进料水503的过量冷凝水508也被输送到排水导管507。在高压洗涤单元502中产生的净化合成气509被提供至高压洗涤单元502下游的第一热交换器518。本文中的术语输送装置被理解为泵和/或压缩机。在高压洗涤单元502中净化第一合成气流301的同时,可以控制净化合成气509的湿度。
在焙烧气体加工单元400中产生的合成气401经由输送装置511输送到饱和塔510。通过输送装置511将合成气401压缩,优选压缩到40巴的压力。输送装置511可包括几个具有中间冷却器的压缩机,该中间冷却器提供合成气401的多级中间冷却压缩。同样,来自气体净化单元600的吹扫气体602也经由输送装置512输送到饱和塔510。通过输送装置512将吹扫气体602压缩,优选压缩到40巴的压力。输送装置512可包括几个具有中间冷却器的压缩机,该中间冷却器提供吹扫气体602的多级中间冷却压缩。饱和塔510是常规的湿式洗涤器,其经由输送装置514提供有来自稍后描述的低温热回收单元524的工艺水513。收集在饱和塔510的贮槽516中的水515用作下述低温热回收单元524中的工艺水。通过饱和塔510将合成气401和吹扫气体602混合,同时将水分添加到所得饱和塔产物气体517中。根据饱和塔的操作参数,即特别是水流和水温,可以控制饱和塔产物气体517的湿度。
将饱和塔产物气体517与净化合成气509一起提供至第一热交换器518。在第一热交换器518中,能量从高温CO变换反应器废气519转移到净化合成气509和饱和塔产物气体517,它们在第一热交换器519的下游合并成合并的合成气流520。通过第一热交换器518中的热交换,相应的高温CO变换反应器废气519被冷却,同时净化合成气509和净化的气流517被加热。优选地,饱和塔510的驱动方式使得合并的合成气流520的水蒸汽与一氧化碳的摩尔比为2.0至3.0,优选2.4至2.6,特别是约2.5。
将合并的合成气流520提供至第一热交换器518下游的高温CO变换反应器521,其中发生上述变换反应。与合并的合成气流520相比,高温CO变换反应器废气519具有降低的水/蒸汽和一氧化碳含量和增加的氢气(H2)含量。高温CO变换反应器废气519-如将在下文中描述-被引导通过几个热交换器以降低其温度,包括第一热交换器518到低温CO变换反应器522,其中发生如上所述的CO变换反应。与进入低温CO变换反应器522的高温CO变换反应器废气519相比,低温CO变换反应器废气523的氢气(H2)含量增加。
低温CO变换反应器废气523被引导通过低温CO变换反应器522下游的低温热回收单元524。在该低温热回收单元524中,低温CO变换反应器废气523的热含量用于提高若干水流的温度。在进入低温热回收单元524之后,低温CO变换反应器废气523随后被引导通过第二热交换器525、第三热交换器526、第四热交换器527、第五热交换器528和第六热交换器529。当通过这些热交换器524,525,526,527,528,529时,低温CO变换反应器废气523的温度稳定地降低,然后作为合成气流530离开低温热回收单元524,并且可选地如有必要,通过空气冷却器531。此后,如上所述,将合成气流530提供至气体净化单元600。
第一,在第二热交换器525中,合成气流530的热含量用于加热将在气化单元300中使用的进料水508。例如,因此可以将该水508从158℃加热至205℃。第二,在第三热交换器526中,水被加热,例如可以用于产生高压蒸汽。例如,将水通常从155℃加热至200℃。第三,在第四热交换器527中,将工艺水513通常从135℃加热至158℃,其用于饱和塔510中。特别是在通过第二热交换器525之后,可进一步使用这种水作为进料水508。在第四热交换器527中,低温CO变换反应器废气523被冷却到其露点以下,因此,大量的冷凝热被释放出来并用于相应的热传递。第四,在第五热交换器528中,将锅炉进料水536通常从35℃加热至155℃,其优选用于制备高压蒸汽。第五,在第六热交换器529中,将水通常从25℃加热至135℃,用于在气化单元300中使烧焦的颗粒201气化。
用于气化单元300的进料水508是如上所述收集在饱和塔510的贮槽519中的水515的至少一部分。收集在饱和塔510的贮槽516中的水515进入第四热交换器527。来自废水处理装置(未示出)的水521可以在通过第六热交换器529之后与水515混合。在第二热交换器527的下游,加热的第四热交换器水流出物(water offstream)533部分用作饱和塔510中的来自低温热回收的工艺水513,并且部分被引导通过第二热交换器525以在第二热交换器525的下游部分用作冷凝水508,部分用作高压洗涤单元502中的进料水503,部分用作焙烧单元200中的工艺水。第六热交换器529下游的另一部分水用作例如提供至水汽提塔的冷凝液534。其他水例如为设备1外部应用而产生的外部高压锅炉进料水535被引导通过第五热交换器528以部分用作锅炉进料水536,例如在气化单元300中和/或用于产生低压蒸汽和/或在焙烧单元200中。锅炉进料水535的另一部分被引导通过到第五热交换器528下游的第二热交换器526。此后,它通过第七热交换器537。
作为设备1的一部分用于将固体废物转化为包含氢气的产物气流的CO变换单元500允许节能地使用低温热回收单元524中的低温热能来加热设备1中使用的工艺水流。
附图标记
1固体废物转化设备
100造粒设备
103城市固体废物
117颗粒
200焙烧单元
201烧焦的颗粒
202焙烧气体
300气化单元
301合成气
400焙烧气体加工单元
401焙烧合成气
500CO变换单元
501变换合成气
502高压洗涤单元
503进料水
504贮槽
505水
506输送装置
507排水导管
508冷凝水
509净化合成气
510饱和塔
511输送装置
512输送装置
513来自低温热回收的工艺水
514输送装置
515水
516贮槽
517饱和塔产物气体
518第一热交换器
519高温CO变换反应器废气
520合并的高温合成气流
521高温CO变换反应器
522低温CO变换反应器
523低温CO变换反应器废气
524低温热回收单元
525第二热交换器
526第三热交换器
527第四热交换器
528第五热交换器
529第六热交换器
530合成气流
531空气冷却器
532水
533第四热交换器水流出物
534冷凝液
535高压锅炉进料水
536锅炉进料水
537第七热交换器
538饱和塔产物气体
600气体净化单元
601富含氢气的产物气体
602吹扫气体
Claims (8)
1.提高固体回收燃料颗粒(117)焙烧的产物气流中氢含量的方法,
其中所述固体回收燃料颗粒(117)被焙烧成烧焦的颗粒(201),同时产生焙烧气体(202),所述焙烧气体(202)被转化为包含氢气和一氧化碳的焙烧合成气(401),
其中将包含所述焙烧合成气(401)的合成气流提供至CO变换单元(500),使至少一部分一氧化碳与水蒸汽反应成二氧化碳和氢气,产生变换合成气(501),
其中将变换合成气(501,523)提供至所述CO变换单元(500)下游的低温热回收单元(524),在所述低温热回收单元(524)中,所述变换合成气(501,523)被引导通过至少两个热交换器(525,526,527,528,529),其中所述变换合成气(523,501)与至少两股水流进行热交换以加热所述至少两股水流,所述至少两股水流在产物气流的生产过程中作为工艺水在相应的热交换器(525,526,527,528,529)的下游使用。
2.如权利要求1所述的方法,其中将变换合成气(530,501)提供至气体净化单元(600)以产生富含氢气、优选具有99.5体积%以上的氢气含量的产物气流(601),同时产生吹扫气体(602),
其中吹扫气体(602)和焙烧合成气(401)均被压缩并且共同地被引入饱和塔(510)以提高所述CO变换单元(500)上游的合成气流(520)中的水含量。
3.如权利要求1或2所述的方法,其中将由烧焦的颗粒(202)气化产生的第一合成气流(301)提供至高压洗涤单元(502)以提高净化的合成气流(509)中的水含量。
4.如前述权利要求中任一项所述的方法,其中所述变换合成气(523,501)在所述低温热回收单元(524)中通过与以下至少一种水流热接触而被冷却:
a)用于对进入CO变换单元的合成气流(509)进行加湿的工艺水流;
b)用于使烧焦的颗粒(202)气化的进料水;以及
c)用于产生高压蒸汽的锅炉水。
5.如前述权利要求中任一项所述的方法,其中在所述低温热回收单元(524)的热交换器(525,526,527,528,529)中,工艺水的压力高于所述变换合成气(523)的压力。
6.将作为固体回收燃料颗粒(117)提供的固体废物转化为富含氢气的产物气流(601)的设备(1),其包括:
焙烧单元(200),其中所述固体回收燃料颗粒(117)可进料,由此可产生焙烧气体(202)和烧焦的颗粒(201);
焙烧气体加工单元(400),其中所述焙烧气体(202)可转化为焙烧合成气(401);
CO变换单元(500),其在所述焙烧单元(200)的下游,可提供有至少包含所述焙烧合成气(401)的合并的合成气流(520),并且其中可产生变换合成气(523,530,501);以及
低温热回收单元(524),其在所述CO变换单元(500)的下游,可提供有变换合成气(523,501),所述低温热回收单元(524)包括至少两个热交换器(525,526,527,528,529),每个热交换器可提供有变换合成气(523,501)和工艺水流以提高工艺水流的温度。
7.如权利要求6所述的设备(1),其还包括饱和塔(510),其中至少所述焙烧合成气(401)的水含量是可调节的。
8.如权利要求6或7所述的设备(1),其中所述低温热回收单元(524)包括以下热交换器(525,526,527,528,529)中的至少两个:
a)第二热交换器(525),其中用于可使烧焦的颗粒(202)气化的气化单元(300)的进料水可由变换合成气(523,501)加热;
b)第三热交换器(526),其中用于产生高压蒸汽的水可由变换合成气加热;
c)第四热交换器(527),其中用于饱和塔(510)的水可由变换合成气(523,501)加热,所述饱和塔(510)用于调节所述CO变换单元(500)上游的至少所述焙烧合成气的水含量;
d)第五热交换器(528),其中用于产生高压蒸汽的水可由变换合成气(523,501)加热;以及
e)第六热交换器(529),其中在可使烧焦的颗粒(202)气化的气化单元(300)中使用的水可由变换合成气(501,523)加热。
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PCT/EP2021/079467 WO2022090122A1 (en) | 2020-10-29 | 2021-10-25 | Co shift unit for the conversion of solid waste into syngas |
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LT3992267T (lt) | 2023-01-10 |
CL2023001205A1 (es) | 2023-12-01 |
KR20230094189A (ko) | 2023-06-27 |
DK3992267T3 (da) | 2023-01-16 |
EP3992267A1 (en) | 2022-05-04 |
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SI3992267T1 (sl) | 2023-03-31 |
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US20240018435A1 (en) | 2024-01-18 |
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IL302307A (en) | 2023-06-01 |
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