CN101812325A - 将固体或液体燃料转化成气体燃料的设备 - Google Patents

将固体或液体燃料转化成气体燃料的设备 Download PDF

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CN101812325A
CN101812325A CN200910260623A CN200910260623A CN101812325A CN 101812325 A CN101812325 A CN 101812325A CN 200910260623 A CN200910260623 A CN 200910260623A CN 200910260623 A CN200910260623 A CN 200910260623A CN 101812325 A CN101812325 A CN 101812325A
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H·魏斯
U·凯莱斯泰乔格鲁
L·基希纳
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Abstract

本发明公开了一种将固体或液体燃料转化成气体燃料的设备。整体煤气化联合循环(IGCC)是用低质量煤高效洁净发电的方法。在气化器和一系列冷却的下游需要进行洗涤步骤以从气化产物(合成气)中提取硫和副产物。由于需要降低CO2排放，如果合成气被转化成氢气而CO2通过另外的洗涤步骤被去除，IGCC技术甚至变得更加吸引人。目前仍然有一些增加合成燃料气中的氢含量的潜能，这有待通过用有限的努力改造涡轮来实现。对于新的项目，对于之后捕获CO2的选择是重要的。气体洁净应该或者能够从一开始处理高的CO2负荷，或者应该可扩充以在之后处理CO2的去除。本发明的目的是Rectisol®洗涤单元的概念，其基于去硫操作能够用少得多的装备扩充来用于以后的CO2去除。

Description

将固体或液体燃料转化成气体燃料的设备
技术领域
本发明涉及将固体或液体燃料转化成含氢气和一氧化碳的气体燃料的设备，其中所述设备至少包括空气分离单元、气化单元、热量回收单元和去硫单元，所述去硫单元与用于对含硫化合物进行脱气的分离器相连。
背景技术
这样的设备用于所谓的IGCC(整体煤气化联合循环)工艺。IGCC是一种发电技术，在该技术中固体或液体燃料被转化成由氢气和一氧化碳组成的气体燃料。将燃料气体用于联合循环来发电。图1显示了气化单元的部件，所述气化单元将气体送入到发电单元。
对IGCC工艺的关键步骤描述如下：
空气分离：空气分离单元ASU为气化单元G提供氧气1。产生的部分氮气2经压缩C得到用于富含氢的燃料气体4的稀释介质3。如果将CO转化成氢气和CO2并将CO2洗出用于螯合时才需要进行氮气稀释。然后氮气提供需要通过发电单元的燃气涡轮(未显示)的质量流。
气化：煤、焦炭或重质液体进料5与氧气1一起被送入到气化单元G，在那里转化成粗合成气。所述合成气由产物和副产物组成，所述产物为氢气和CO，所述副产物如CO2、COS、H2S和甲烷以及痕量组分，根据给料所受的污染如羰基铁、羰基镍、羰基钒、氨气、含汞化合物、含砷化合物或其它。该合成气的压力通常为40-60bar，将该合成气在气化单元G中冷却到约280℃。在冷却步骤中产生的高压蒸汽6被送入到过热器H中，并可在发电单元的蒸汽涡轮(未显示)中使用。
CO转化：根据燃气涡轮的能力和对CO2排放的要求，CO转化步骤是该工艺的一部分。如果CO2排放必须最小化，冷却的合成气7在CO转化单元S内被转化，大部分CO被转化成氢气和CO2。
热量回收：为了清洗经转化的气体8，气体温度必须降低至接近环境温度。这在热量回收单元R中通过产生蒸汽9，加热锅炉给水并最终以与空气或冷却水相反的方向冷却气体来实现。分离的水被循环到气化单元G或CO转化单元S中。
去除硫和CO2：洗涤系统A的主要任务取决于IGCC设备的特点。如果该工厂可以无限制地排放CO2，则洗涤系统A的主要任务是在被送入燃气涡轮之前，从经转化和冷却的合成气10中去除含硫成分。在这种情况下，企图在合成气中含有尽可能多的CO2以使高质量流进入到燃气涡轮中。所述含硫成分被用作Claus设备K的进料气体11。在CO2也必须从合成气10中去除的情况下，洗涤系统A看起来就完全不同了。将其构造设计从一种换成另一种是非常昂贵的，因为很多装备都必须更换。
发明内容
本发明的目的是提供一种设备，在之后出现额外的去除CO2的要求时，可以再利用尽可能多的装备。
实现该目的的方式是使用于对含硫化合物进行脱气的分离器准备好在上方增设用于CO2去除的洗涤单元。
本发明的其它有利实施方案在从属权利要求中被限定。
附图说明
图1显示了现有技术中IGCC的气化单元的部件。
图2显示了用于从合成气F中去除CO2和硫的
Figure G2009102606231D00021
工艺的简化流程图。
图3详细地显示了根据本发明的示例性实施方案的
Figure G2009102606231D00022
单元，其中CO2和/或含硫成分可被甲醇吸收，并从含一氧化碳和/或氢气的进料气体中除去。
具体实施方式
下面将描述新的气体净化方法的特征。
该方法的目的是节省IGCC项目的投资成本，所述IGCC项目是为捕碳做准备，但仅实施第一阶段的硫去除，这可能意味着多年的实施周期。将这分成两个阶段的原因是：燃气涡轮不可用于富含氢的燃料实施，在获得螯合能力之前就需要发电，地方规章在某个固定日期之前允许CO2排放等。本发明提供一种灵活的解决方案，最大程度上利用第一阶段的投资，但不需要不能收益的资本和运作费用。
由于其显著的去除硫和CO2以及所有相关痕量成分(金属羰基化合物、HCN)的能力，所谓的
Figure G2009102606231D00031
洗涤被推荐为优选的工艺。是一种用有机溶剂(通常是甲醇)在零度以下的温度去除物理酸性气体的工艺。
Figure G2009102606231D00033
能净化合成气达到在ppm范围内的总硫(包括COS)和CO2为0.1vppm。
该工艺的主要优势是较低的动力消耗指标值，使用便宜的易获得的溶剂，以及工艺构造上的灵活性。
图2显示了用于从合成气F中去除CO2和硫的
Figure G2009102606231D00034
工艺的简化流程图。CO2和含硫化合物被单独去除，导致得到纯的CO2产物CO2和富含H2S/COS的Claus气体馏分C。
由于该工艺的物理属性，高压和高的酸气浓度是特别有利的。因此
Figure G2009102606231D00035
经常用于净化在残渣油、煤或褐煤气化下游的经转化、部分转化或未转化的合成气。从基于IGCC的发电厂的气化单元得到的合成气在组成上是类似的，但对于气体纯度的要求没有平常化学工艺所要求的那么高。
对于在IGCC中的这个新方法，提议两步实现
Figure G2009102606231D00036
洗涤单元。在第一步(情况1)中可以仅对合成气脱硫，
Figure G2009102606231D00037
洗涤留下最大量的CO2。在第二步(情况2)中，除了含硫成分之外，在
Figure G2009102606231D00038
洗涤单元中还可从合成气中除去CO2。
下面详细描述两步安装
Figure G2009102606231D00039
洗涤单元的概念。
为了将情况1的投资变为足可支撑的投资，情况1中安装的所有装备也应该可用于情况2，使得仅需要添加新的装备。因此，对于情况1的
Figure G2009102606231D000310
单元的投资成本显著低于回收硫和CO2的大型
Figure G2009102606231D000311
单元。根据预算估计，差别为约25％。类似地，运行成本将低于大型工厂的，尽管一些装备需要为情况2进行尺寸改造以避免装备类似。然而，在将情况1的构造改造成情况2的构造之后所花费的总钱数高于从一开始大型设计所需要的钱数。
为了更好地理解本发明，下面根据图3所显示的示例性实施方案来进行更详细的解释。
图3显示的是
Figure G2009102606231D00041
单元，其中CO2和/或含硫成分可被甲醇吸收，并从含一氧化碳和/或氢气的进料气体中除去。
在图3中，所有情况1需要的装备以实线画出，而为情况2待添加的装备用虚线画出。改造所需要的所有阻断阀门都显示了出来，在情况1中打开而在情况2中关闭的那些为黑色，在情况2中打开而在情况1中关闭的那些为白色。为了在操作上从情况1变到情况1时最小化系统的停工期，大多数阀门都必须在情况1中都已安装好。
工艺步骤如下：
情况1：仅对进料气体脱硫
1.进料气体预冷却：
因为是在低于0℃的温度下进行吸收，进料气体1在进料气体冷却器E1中以与工艺流2和3相反的方向进行预冷却。为了避免包含的水凝固和形成水合物，将冷的甲醇4注入到进料气体1中，在冷却步骤之后将得到的液体甲醇/水混合物5在分离鼓D1中分离。螺旋卷式热交换器E1已经装备有情况2的CO2气流41所需要的通道。将经预冷却的进料气体6送入到吸收塔A中。
2.从进料气体中去除H2S：
对于情况1，仅需要去除硫，这在吸收塔A中完成。经冷却的进料气体6进入到吸收塔A的底部，并向上流动。逆流的甲醇7从上流下并溶解含硫成分以及少量的CO2。因为必须除去吸收热，将部分负载的甲醇8在热交换器E2中以与外部冷却介质相反的方向冷却回，并送入到吸收塔A中。负载硫的甲醇9从底部离开塔A，而经净化的气体流3从顶部取出。气体流3在进料气体冷却器E1中以与进料气体1相反的方向被加热，并送到边界线作为气体产物43，所述气体产物可用作燃气涡轮(未显示)的燃料气体。
3.中间甲醇膨胀：
将离开吸收塔A的负载硫的溶剂9在热交换器E3中以与离开吸收塔A的净化气体3相反的方向被过冷却，并膨胀到分离鼓D2中达到约10bar(a)的中间压力，以回收被共吸收的氢气和一氧化碳。为了增加该工艺的总回收率，将含有氢气和一氧化碳的气体流10在循环压缩机P1中再压缩，并返回到进料气体1中。对于情况2，也将负载CO2的甲醇流11部分膨胀，得到的从分离鼓D3的顶部离开的闪发气体12也进入循环压缩机P1中。根据总的工厂设备能力，循环压缩机P1可能必须为情况1的全流量能力来设计。
4.生产冷H2S馏分：
将负载的甲醇14与在工艺步骤5中得到的含H2S的气体13一起膨胀到分离器S1中接近环境压力以回收H2S(和共吸收的CO2)。该闪蒸通过在热交换器E4中以与贫甲醇16相反的方向加热液相15来得到支持。从分离器S1的顶部取出含CO2的H2S馏分2，该馏分在进料气体冷却器E1中以与进料气体1相反的方向被加热，并作为进料17送至Claus单元(未显示)中用于硫回收。
5.热再生：
用泵P2将仍然负载的溶剂18从分离器S1的底部取出，并在热交换器E5中以与热贫溶剂16相反的方向加热，然后将其膨胀到分离鼓D4中，在那里被分离成液相19和气相13。然后液相19在热交换器E6中被加热，并送入到热再生塔H中。
6.生产热H2S馏分：
热的负载溶剂19从顶部进入到热再生塔H中。在这里，所有残余的含硫成分通过甲醇蒸气被汽提掉，所述甲醇蒸气是通过再沸器R1在塔H的底部产生的。通过水冷却的内部冷凝器E7在塔H中产生回流。
从热再生塔H的上空离开的具有环境温度的H2S馏分20被直接送到Claus单元(未显示)用于硫回收。
从热再生塔H的底部离开的贫甲醇21被分离成两个馏分16、22。馏分16在甲醇/甲醇热交换器E6、E5和E4中被冷却，并泵送回甲醇洗涤塔A中。贫溶剂16的一小部分4被注入到进料气体冷却器E1上游的进料气体流1中。
7.甲醇/水分离：
将由分离鼓D1得到的冷凝物23，即甲醇和水的混合物，在热交换器E8中以与贫甲醇流22相反的方向被加热。然后，将两股流22、23都送入到甲醇/水分离塔W中，在那里它们被分离成甲醇24和水25。甲醇蒸气24被送回到热再生塔H中，而水25作为废水处理。为了产生汽提蒸气，分离塔W配有再沸器R2。
总结：
所有装备都必须具有足够的能力不进行改变而用于情况2。除了上面指出的装备，这主要涉及5和7中描述的装备。
情况2：对于去除CO 2 额外需要的装备
11.吸收塔A的扩充
必须添加用于从气体流26中去除CO2的吸收塔C。负载CO2的溶剂27从吸收塔C的底部被泵送到吸收塔A的顶部，在那里被用作洗涤剂。热交换器E2现在与吸收塔C相连。该塔实现为单独的装备，与吸收塔A相邻。
12.循环：
将不需要在吸收塔A中用作洗涤剂的、从吸收塔C得到的负载CO2的甲醇28在热交换器E9中过冷却，并膨胀到分离鼓D3中达到与负载的甲醇流9相同的中间压力。含氢气的闪发气体12被送至压缩机P1中，并循环到进料气体1中。
13.产生CO2：
第一CO2产物29将在高压下被回收。为此，使用分离器S1以及第二分离器S2。在分离器S1中产生的富含CO2的含硫气体流30被膨胀到分离器S2中进行脱硫。含硫成分通过来自分离鼓D3的负载CO2但不含硫的甲醇馏分32的一部分31被洗涤回来。脱气CO2直接贡献给CO2流33，该CO2流在进料气体冷却器E1中以与进料气体相反的方向被加热，并送至边界成为CO2产物29。
14.H2S增浓：
为了得到低压CO2产物34，甲醇流35、36以及来自分离器D4的气相37膨胀到H2S增浓塔T中。在塔T的上部用负载CO2但不含硫的甲醇馏分32的另一部分38对上方气体进行脱硫。为了增加H2S馏分20中的H2S浓度以及增加CO2产物34的流速，将排液槽的溶剂39再膨胀到塔T下部的一体化分离器D5中。用压缩机P3将所得CO2闪发气体40再压缩到塔T中。
CO2流41在进料气体冷却器E1中以与进料气体1相反的方向被加热，并送至边界成为CO2产物34。
富含H2S的甲醇流42从塔T中取出，并通过电力线15和42引入到热交换器E4和E9中进行加热，然后将其膨胀到分离器S1中。
剩余的工艺步骤(5-7)操作与情况1类似。
为了节省情况1中的操作用电，建议安装一个仅具有情况1所需要的泵流量的主溶剂泵P4，并平行安装另一个泵P5用于情况2中增加的甲醇流。
对于外部的制冷设备(未显示)推荐类似的工艺：安装一个单元仅用于情况1；为了适应情况2需要第二个相同的制冷单元。
物料衡算：
表1、2和3的数据源自于使用煤原料的GE气化工艺的典型工艺气体。为了根据情况1的操作，留下约70％的CO2。该工艺保证经处理的气体中总硫含量最大0.1vppm。
如上所述，情况1产生两个含硫酸性气体馏分17和20。其中一个20具有高浓度H2S；另一个17仅具有低浓度。这两个馏分可混合成一个馏分被送到硫回收设备中或者被单独进一步处理。
物料衡算情况1(表1)：
系统的进料气体从气化器中出来时未发生转化。进料中高含量的CO被转化成净煤气，在燃气涡轮中燃烧。进料气体中的CO2仅部分去除(留下70％CO2)。因此，燃气涡轮尾气含有高负荷CO2。
物料衡算情况2(表2)：
系统的进料气体现在酸性转化单元中被转化为约2.0mol％的CO含量。净煤气含有该CO和5.8mol％CO2(留下的CO2小于10％)。这使得最终燃气涡轮尾气中具有非常低负荷的CO2。
动力消耗指标(表3)：
表3显示了情况1和2中能量和物料的消耗数据。
表1
Figure G2009102606231D00081
表2
Figure G2009102606231D00082
表3
 情况1   情况2
  在-40℃下制冷(热量)   MW   9.0   17.25
  LP蒸气(5bara，sat)   t/h   7.3   22.0
  MP蒸气(10bara，sat)   t/h   9.3   13.8
  电能泵   kW   2175   4095
  电能压缩机   kW   850   2305
  冷却水30℃＝＞40℃   m3/h   330   750
  甲醇损失   kg/h   245   190

Claims (6)

1.将固体或液体燃料转化成含氢气和一氧化碳的气体燃料的设备，其中所述设备至少包括气体分离单元、气化单元、热量回收单元和去硫单元，所述去硫单元与用于对含硫化合物进行脱气的分离器相连，其特征在于，使所述用于对含硫化合物进行脱气的分离器准备好在上方增设去除CO2的洗涤单元。
2.权利要求1的设备，其特征在于，使所述去硫单元准备好另外与CO2吸收塔相连，所述CO2吸收塔被插在该去硫单元和所述用于对含硫化合物进行脱气的分离器之间。
3.权利要求1或2的设备，其特征在于，使所述用于对含硫化合物进行脱气的分离器准备好另外与待添加的H2S增浓单元相连。
4.权利要求1-3之一的设备，其特征在于，所述去硫单元为使用有机溶剂去除物理酸性气体的吸收塔。
5.权利要求1-4之一的设备，其特征在于，待添加在所述用于对含硫化合物进行脱气的分离器上方的所述洗涤单元为使用有机溶剂去除物理酸性气体的吸收塔。
6.权利要求2-4之一的设备，其特征在于，待插在所述去硫单元和所述用于对含硫化合物进行脱气的分离器之间的所述CO2吸收塔为使用有机溶剂去除物理酸性气体的吸收塔。
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