CN102549116B - 向气流床气化反应器供应含碳燃料的方法 - Google Patents
向气流床气化反应器供应含碳燃料的方法 Download PDFInfo
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Abstract
本发明涉及一种向气流床气化反应器供应含碳燃料以在加压及高于灰分的熔化温度的条件下生产含CO、H2及飞灰的气体的方法，其中将所产生的气体输送至进一步的处理阶段，尤其是至少一个合成阶段，此种方法应以成本有利及简单的方式提高液态产物的产量。这通过如下实现，使用由下游处理阶段产生的还含有碳氢化合物和/或氢的废气将燃料气动输送至气流床气化反应器。
Description
技术领域
本发明涉及一种向气流床气化反应器供应含碳燃料以在加压及高于灰分的熔化温度的条件下生产含CO、H2及飞灰的气体的方法，其中将所产生的气体输送至进一步的处理阶段，尤其是至少一个合成阶段。
背景技术
在用含二氧化碳、一氧化碳及氧的气体将微粒状至粉尘状的燃料卸料和输送到处于加压下的气流床气化器内的情况下，在气流床气化器内磨细的或粉尘状（<0.5mm）的燃料（例如煤、石油焦、生物废弃物）或低粒子负荷（<50kg/m3）的悬浮形式的燃料与含氧的气化剂于最高达10MPa的提高的压力下及高于炉渣熔点的温度下反应时，应输入低于化学计量比例的含氧气体，从而产生含一氧化碳的产物气体。在此作为实例提及EP0333991A1或DE102007020333A1。
由于燃料原本是处于环境压力，因此必须先经由输入系统将压力升高至高于反应器压力的压力水平，以便计量配料式输送至高压气化反应器的燃烧器。
一种有利的方法设计为，将燃料从储存容器输送到锁斗。这些锁斗首先被加压至高于反应器压力的压力水平，以便接着经由输送管线将燃料以密流输送的方式输送到用于气化反应器的燃烧器的始终处于加压的储存容器中。由该储存容器连续地分别将经配料的燃料物流供应给燃烧器。密流输送所需的运输气体是在锁斗的出口处或出口处附近被输入，或是被输入输送管线。然后将排空的锁斗卸压，以便能够在接近大气压力的压力状态下接纳进一步的燃料进料。将卸压气体除尘，并排放到大气中。
通常使用来自空气分离设备的氮或是利用二氧化碳来进行卸料。 如果要生产贫氮的合成气体或氢和/或CO，则使用二氧化碳。
可以在气化后的气体处理过程中获得二氧化碳。通常是将从气化器流出的气体进行除尘及净化，然后进行CO转化，以根据合成所需的H2/CO比例进行调整，或是产生纯氢。在此将CO及水蒸气转变为CO2。接着将气体冷却、冷凝出水分、然后在洗涤过程中用循环溶剂（例如，MDEa、Genosorb、甲醇）将CO2洗出。接着在解吸器中通过降压或升温将CO2从溶剂中分离出来。
以此方式获得的气体除了含有CO2外，还含有其他成分，例如H2、CO、N2、甲烷、硫化氢、氩、所使用的溶剂（例如甲醇）的蒸气等，尤其是，CO的含量为例如0.1%。虽然可能的是，在洗涤过程中进一步降低了有害物质的含量，但是耗费（投资成本及操作成本，例如用于蒸气及电力的消耗）随着对纯度要求的提高而快速攀升。
DE10 2007 020 333 A1描述一种用于操作煤尘加压气化的粉尘进给系统的方法，该系统包括储料斗、粉尘进给锁斗及配料容器。由此，向储料斗中输入作为惰性稀释剂（inertisierungsmittel）及松散剂的经加热的氮，与此相对地，用纯二氧化碳对锁斗施压并输送粉尘。来自锁斗的卸压气体被卸压，然后在过滤器中脱除固体。在此利用重力流将经加压的锁斗排空至配料容器。
以上提及的已知解决方案的缺点尤其在于，用于卸料及流化的气体只允许含有低浓度的环境有害物质CO、H2S、甲醇等，因为这些气体它们会被排放到大气中。容器相互叠置的以重力流为基础的卸料方式，由于构造高度高而很耗费，并且由于堆料的压实而被证实操作不够稳定。尽管有很多不同的方式，但证实非常困难的是，经济地进行使得堆料中的内应力保持足够低的容器加压过程。
为了提供一种确保以经济的方式用于向加压气化装置供应燃料的方法，该方法使得来自煤卸料和运输的有害物质排放最小化或完全避免，在申请人等的未公开的DE10 2009 006 384中提出，将燃料借助特定气体混合物从储存容器输送到锁斗。
为了在排放到大气中之前对污染输送气体的有害物质（例如CO、 甲烷、硫化氢、所使用的溶剂(例如甲醇)的蒸气等)进行相应的处理，在该申请中建议将二氧化碳与氧混合作为卸料运输气体，并将其催化氧化。
经净化的合成气体可用于液态碳氢化合物的合成，例如用于费托合成法或MTG合成法(甲醇至汽油)中，在MTG合成法中，在第一步骤中生产甲醇，在第二步骤将甲醇转变成汽油。这两种方法中都产生主要由碳氢化合物组成的气态副产物。在这两种方法中，对液态产物进行处理都需要氢，例如通过在PSA设备(变压吸附过程)中分离而生产氢，其中产生主要包含CO及H2的残余气体。
现有的MTG技术：将一部分气态副产物非连续地用于MTG催化剂的再生，剩余量被输出。如果MTG反应器的数量较少，则将气体收集在一起，以便在再生期间可以产生足够的热功率。缺点：需要收集容器(除了生产以外的其它要求)，碳将以CO2的形式被排放到大气中，而不是被构入反应产物中。
此种方法的基本优点(副产物的回输及液态产物产量的提高)是已知的，但是气态副产物的压缩及回输会造成以下的问题：
--其量对旋转式径向或轴向压缩机而言通常过少，而活塞式压缩机则具有数倍的较高的维修需求；
--组成及量波动。因为碳氢化合物具有是氢密度多倍的较高密度(CH4是8倍，C5H12是36倍)，并具有较低的等熵系数，因此混合物的特性及旋转式压缩机的输出压力变化。当氢含量暂时升高并因而气体密度低时，旋转式压缩机提供的压力明显较低，该压力对于将气体进料至气化器而言可能太低；
--一部分碳氢化合物在压缩过程中冷凝；
--在气化器内需要进料通道，在不存在副产物时必须冲洗该进料通道。
发明内容
本发明的目的是，成本有利地并以简单的方式提高液态产物的产 量。
根据本发明用开篇所述类型的方法如下实现了上述目的，使用由下游处理阶段产生的还含有碳氢化合物和/或氢的废气将燃料气动输送至气流床气化反应器。
本发明的其他实施方式由从属权利要求提供。在此，特别是设计为进一步的处理阶段由以下形成：CO转化阶段、气体净化阶段及第一合成阶段，例如用于甲醇的合成、以及第二合成阶段，例如MTG(甲醇至汽油)阶段，其中回输的气体至少含有1体积％的碳氢化合物和/或1体积％的氢。
本发明的优点尤其在于，将合成过程(例如甲醇合成及MTG合成)的气态或气化的副产物与二氧化碳(CO2)混合，由此提高气体量，并使气体的特性稳定化，因此可以使用旋转式压缩机。这样选择二氧化碳的量，使得在压缩过程中避免碳氢化合物冷凝。在此，可以使用负载有有害物质的CO2级分，由此可以取消常规情况所必需的CO2处理。
本发明的另一个优点在于，以经压缩的气体混合物取代纯的输送气体来稀释输送入气化器的固体燃料，其中，另外同样也可以利用气体混合物将燃料从锁斗输送到储存容器，其中优选用喷射器将卸压气体回输，以避免释放含H2、CO、及碳氢化合物的气体。
本发明还设计为，从下游设备回输的气体在压缩前与CO2混合。
在实施方式中还设计为，将在气体处理中获得的主要包含CO2并包含至少10ppm的H2S和/或CO的气体混入含有碳氢化合物和/或氢的回输气体中，其中还可设计为，将回输气体至少部分地用于储存容器内的燃料输送，以在储存容器内形成压力，和/或用于使储存容器内的燃料流化。
实施方式
根据以下描述以及附图对本发明的其他优点、细节及特征做进一步的说明。所述附图展示了根据本发明的气化方法的示意图。
在整体用1表示的设备中，来自储存容器2的粉尘状燃料经由连 接管线2c被转移至锁斗3。为了能够容纳燃料，必须首先将锁斗3卸压。将从锁斗流出的气体3e除尘，并被排放到大气中。接着用燃料填充锁斗，并用气体3a及3b施压。然后用3c冲洗锁斗的输出管线，并将粉尘状的燃料从锁斗3经由管线4输送至储存容器5。在此过程中输入松散气体和流化气体3b及运输气体4a。储存容器5始终处于工作压力，并经由多条管线6连续地向气化过程7供料。
通过吹送松散及流化气体5b进行从储存容器到储存容器的出口区的输送，并借助另外的运输气体5c进行到燃烧器管线6的输送。燃料流6经由燃烧嘴7a连续且受控地以气动方式(优选以密流输送的方式)输送至气化过程7。利用喷射器14将来自储存容器的卸压气体5e回输。
气化过程7包括气化反应器、气体冷却过程和除尘过程、以及炉渣7b及含固体的水的冷却及卸料。在CO转化过程8中一部分一氧化碳及水蒸气被转化成二氧化碳及氢。接着在气体净化过程9中用溶剂(如甲醇)将气体净化，以及将二氧化碳从合成气体(主要为H2及CO)分离出来。在气体净化过程中获得的含二氧化碳的气体具有低压力，而且通常含有少量的有害物质(例如一氧化碳＜1％，硫化氢＜10ppmv)及痕量的碳氢化合物。所获得的二氧化碳可以具有一种或多种品级。
附图展示了贫有害物质的CO2流9a及负载有有害物质的物流9b，它们被分开压缩。通常被洗出的CO2量大于固体卸料和输送所需的CO2量，因此另外的CO2流离开气体净化过程9。经净化的合成气体在10中转变成甲醇，以及在MTG合成过程(11)中被转变成汽油11b和LPG11c。对于液态产物的处理而言氢通常是必需的，氢是在12中通过分离(例如用PSA法)获得的。副产物11a、卸压气体10a、以及残余气体12a被送入压缩机13内适当的压力级，并且根据本发明经由物流13a或13b回输。这些物流以附加有小点的直线表示。
为了起动整套设备，需要进口气体，例如CO2或氮。通常优选使用氮，为此目的，可以液态来储存氮。一旦设备运转到二氧化碳在气体净化过程被分离出来时，对于正常运转而言，就切换到含二氧化碳 的气体，在合成过程10及11开始运转后，向含二氧化碳的气体中混入其他气体。
作为可替代的方法实施方式，考虑如下：
--气体10a，11a，12a中的仅一种，或其中的两种或多种级分具有不同的压力；
--进料4a、5a、5b的一些含有卸料气体3d；
--回输的含CO、H2、CnHm的气体13b用于5c，这样为了排放原因的喷射器14就没有必要了；
--回输的含CO、H2、CnHm的气体13b也作为卸料气体3d。可使用显著较多的气体，但是必须将卸压气体净化或是收集到气体缓冲器中，并例如用压缩机13压缩；
--由于卸料气体3d具有较高的压力，因此也作为喷射器14用的动力气体13a。
除了上述的实施例外还可以设计为，锁斗的数量可以更多，并且可以使用多个压缩机来进行用不同压力产生的多级压缩。
Claims (6)
1.一种向气流床气化反应器供应含碳燃料以在加压及高于灰分的熔化温度的条件下生产含CO、H2及飞灰的气体的方法，其中将所产生的气体输送至进一步的处理阶段，使用由下游处理阶段产生的还含有碳氢化合物和/或氢的废气将燃料气动输送至气流床气化反应器，其特征在于，
进一步的处理阶段由以下形成：CO转化阶段、气体净化阶段及第一合成阶段，以及第二合成阶段，其中回输的气体至少含有1体积%的碳氢化合物和/或1体积%的氢，并且其中从下游设备回输的气体在压缩前与CO2混合。
2.根据权利要求1的方法，其中所述的进一步的处理阶段为至少一个合成阶段。
3.根据权利要求1的方法，其中所述第一合成阶段用于甲醇的合成。
4.根据权利要求1的方法，其中所述第二合成阶段是MTG（甲醇至汽油）阶段。
5.如权利要求1的方法，其特征在于，将在气体处理中获得的主要包含CO2并包含至少10ppm的H2S和/或CO的气体混入含有碳氢化合物和/或氢的回输气体中。
6.如权利要求1或5的方法，其特征在于，将回输气体至少部分地用于储存容器内的燃料输送，以在储存容器内形成压力，和/或用于使储存容器内的燃料流化。
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| DE102013018332A1 (de) * | 2013-10-31 | 2015-04-30 | Linde Aktiengesellschaft | Vorrichtung zur Einbringung von festem organischen Einsatzmaterial in eine Vergasungsanlage |
| CN104560209B (zh) * | 2014-12-31 | 2017-08-01 | 神华集团有限责任公司 | 排渣装置、包括其的多元浆气化装置及排煤渣方法 |
| CN110234671B (zh) | 2017-01-31 | 2022-05-31 | 巴斯夫欧洲公司 | 在多元醇中的氧化硅颗粒分散体 |
| EP3485961B1 (de) | 2017-11-16 | 2023-09-13 | L'air Liquide, Société Anonyme Pour L'Étude Et L'exploitation Des Procédés Georges Claude | Waschkolonne zur reinigung von gasströmen |
| CN109694750A (zh) * | 2019-02-20 | 2019-04-30 | 科林未来能源技术(北京)有限公司 | 一种综合利用的气化炉排渣系统 |
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- 2010-08-10 UA UAA201202485A patent/UA102921C2/ru unknown
- 2010-08-10 CA CA2770533A patent/CA2770533A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5132007A (en) * | 1987-06-08 | 1992-07-21 | Carbon Fuels Corporation | Co-generation system for co-producing clean, coal-based fuels and electricity |
| CN1362986A (zh) * | 2000-02-29 | 2002-08-07 | 三菱重工业株式会社 | 生物质气化炉和利用通过生物质气化所得的气体的甲醇合成系统 |
| WO2008132069A2 (de) * | 2007-04-30 | 2008-11-06 | Siemens Aktiengesellschaft | Einsatz von reinem kohlendioxid als inertisierungs- und fördermedium in staubeintragsystemen für die kohlenstaubdruckvergasung |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102549116A (zh) | 2012-07-04 |
| US20120137583A1 (en) | 2012-06-07 |
| US8932375B2 (en) | 2015-01-13 |
| WO2011018198A3 (de) | 2011-07-07 |
| TW201109590A (en) | 2011-03-16 |
| CA2770533A1 (en) | 2011-02-17 |
| KR20120052982A (ko) | 2012-05-24 |
| DE102009036973A1 (de) | 2011-02-17 |
| WO2011018198A2 (de) | 2011-02-17 |
| EA021013B1 (ru) | 2015-03-31 |
| WO2011018198A4 (de) | 2011-08-25 |
| EP2464712A2 (de) | 2012-06-20 |
| EA201200263A1 (ru) | 2012-09-28 |
| AU2010281841A1 (en) | 2012-03-08 |
| UA102921C2 (ru) | 2013-08-27 |
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