CN1872388A - 用于混合psa/tsa系统的改进的控制方案 - Google Patents

用于混合psa/tsa系统的改进的控制方案 Download PDF

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CN1872388A
CN1872388A CNA2006100793333A CN200610079333A CN1872388A CN 1872388 A CN1872388 A CN 1872388A CN A2006100793333 A CNA2006100793333 A CN A2006100793333A CN 200610079333 A CN200610079333 A CN 200610079333A CN 1872388 A CN1872388 A CN 1872388A
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W·P·舒密特
D·P·茨威林
A·D·怀特
M·A·卡尔巴斯
C·J·濑斯维尔
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Air Products and Chemicals Inc
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Abstract

提出一种用于从进料气体中除去水及二氧化碳(CO2)的吸附工艺的改进的控制方案，其利用温度变换(即TSA)及压力变换(PSA)的结合来再生吸附剂。该控制方案包括，调节由再生气体提供的热量，该热量是作为取自水选择性吸附区的关键部位的温度数据的函数。该关键部位相当于由温度变换再生到由压力变换再生所预期的转变位置。在本发明的优选实施方案中，也按照进料气体水含量的函数进行再生热量的调节。

Description

用于混合PSA/TSA系统的改进的控制方案
发明背景
本发明涉及一种用于从进料气体中除去水及二氧化碳(CO2)的吸附工艺，该工艺使用了温度变换(即TSA)及压力变换(PSA)来再生吸附剂。更具体而言，本发明涉及一种工艺，其中：
(a)该工艺采用具有用于引入进料气体的进料口以及用于排出产品气体的产品口的吸附容器；
(b)位于邻近于进料口的是含有用于从进料气体中吸附水的水选择性吸附剂(特别是活性氧化铝或硅胶)的水除去区；
(c)位于水除去区与产品口之间设置含有用于从进料气体中吸附CO2的CO2选择性吸附剂(特别是分子筛)的CO2除去区；
(d)该工艺在吸附工序与再生工序之间循环；
(e)在吸附工序中：
(i)进料气体从进料口开始流经该容器；
(ii)至少一部分水选择性吸附剂用水饱和；
(iii)至少一部分CO2选择性吸附剂用CO2饱和；且
(iv)产品气体从产品口排出；
(f)在再生工序中：
(i)将容器减压至较低压力；
(ii)加热的再生气体从产品口开始流经该容器，提供一些再生热以解吸(即通过温度变换)基本上全部在吸附工序中吸附的CO2和部分(但不是全部)解吸在吸附工序中吸附的水；且
(iii)冷却的再生气体从产品口开始流经该容器，解吸(即，通过压力变换)大部分或基本上全部在吸附工序中吸附的残留水份；且
(iv)用进料气体增压该容器使该容器为下一个吸附工序作好准备。
以上“混合(hybrid)”TSA/PSA工艺(下文称为混合工艺)是已知的。具体可参见Kalbassi等人(下文称为“Kalbassi”)的美国专利6,599,347，其教导了有关垂直吸附容器的混合工艺，在该容器中，进料口位于容器的底部，且进料气体在到达位于容器顶部的产品口前向上流动。
混合工艺的关键问题在于，精确计算上述(f)(ii)中所需的由加热的再生气体提供的热量，以便除必要之外，不浪费能量来加热再生气体。正如本领域技术人员所能了解的，由加热的再生气体提供的热量必须足以推动所产生的热脉冲经过CO2除去区，以使它在水除去区内的某位置(下文称为设计位置)失效，该位置要足够远，以致于可以再生大部分的水除去区(即通过温度变换)，但没有进入水除去区太远，以致于没有充分利用冷却的再生气体实现水除去区再生(即通过压力变换)的能力。换句话说，设计位置所对应的是位于水除去区内，由温度变换再生向压力变换再生发生转换的位置。
Kalbassi通过调节由被加热的再生气体提供的热量，解决了混合工艺中所存在的这个关键难题，所述热量是进料气体水含量的函数。与基于可能遇到的最不利的环境条件确定固定的热量不同的是，这提供显著地能量的节省。然而相对于本发明，Kalbassi的方案是不完善的，与本发明不同，Kalbassi对必要的热量的调节，没有考虑在再生工序中的温度数据及取自以设计位置为中心的水除去区的关键部位(关键部位)内的具体温度数据。该温度数据可以使人们测得热脉冲失效的确切位置，且通过适当调节下一个再生工序中提供的热量，该温度数据可以使与设计位置有关的偏差一致。以这种方式，从一个周期到一个周期，对所提供热量的调节的调整能力进一步在Kalbassi方案中提高了能量的节约。
通常，关键部位会是水除去区中除了边缘或接近边缘的部位之外的任何部位，正如本领域技术人员所能了解的，由于CO2吸附剂水污染的风险，所以在混合工艺中水除去区的边缘不是热脉冲失效的实际设计位置。(具体而言，如果接近水除去区边缘的设计位置邻近于CO2除去区，则意味着水除去区通过温度变换来实现再生即使有，也很少的；同样地，如果接近水除去区边缘的设计位置在引入进料气体处，则意味着水除去区通过压力变换来实现再生即使有，也很少)。更确切地说，如果人们考虑在水除去区中水选择性吸附剂被装填为相同厚度的10层(层1开始于与进料口相邻的水除去区的一端，接下来依次到层10，层10与CO2除去区相邻)，关键部位将包含层2到层9之间含端值的任何3-4个连续层。已知在典型的混合系统中，热脉冲失效的设计位置一般位于层6到层9之间的某个部位，由此可以判断关键部位通常包含层6到层9。
由Monereau等人转让给L’Air Liquide的USP6,402,809(2002)也公开了以上提及的混合工艺。Monereau进一步教导了根据操作条件控制再生气体的温度，该操作条件包括“在再生结束时由[吸附器]热前缘输出的热分布图”。或者，Monereau在第5栏第5行更具体地进行了教导，当“热前缘离开[水除去区]热前缘”时，根据热分布图控制再生气体的温度。因此，温度数据取自水除去区的边缘，它对应于本发明水除去区定义中的层1。如前面所讨论过的，这与本发明的教导不同。具体而言，该位置意味着即使利用了水除去区容器压力变换来实现再生的能力，也很少，因此对再生气体的加热十分必要。
由Bosquain等人转让给L’Air Liquid的USP4,541,851(1985)教导了在上述混合工艺中，使用径向吸附床，在该混合工艺中，进料口将进料气体分布于吸附容器的外围，且进料气体在到达位于容器内部的产品口前，沿径向向内流动(如Kalbassi所述，首先通过水除去区，然后通过CO2除去区)。为了解决该形状对与吸附与再生工序之间的温度波动相关的机械应力问题的灵敏度，Bosquain教导了采用在极靠近水除去区(即：也对应于本发明定义的水除去区中的层1)的进料端的外侧格栅上设置的温度传感器，以防止在再生期间所产生的热脉冲到达外侧格栅。
由Christel等人转让给Pall Corporation的USP4,832,711(1989)教导了使用吸附剂从进料气体中吸附水来储存吸附工序所产生的热量，用于加热再生气体，在吸附工序中测量通过吸附剂的热脉冲的前进值，以使所产生的热脉冲在离开床层的产品端之前，停止吸附工序。Christel的方案没有外部加热再生气体。因此本发明所解决的问题(即：精确确定在再生期间需要提供的外部热量)在Christel的方案中没有专门提到。
发明简述
本发明是一种用于从进料气体中除去水及二氧化碳(CO2)的吸附工艺的改进的控制方案，其利用温度变换(即TSA)及压力变换(PSA)的结合来再生吸附剂。该控制方案包括，调节由再生气体提供的热量，该热量是作为取自水选择性吸附区的关键部位的温度数据的函数。该关键部位对应于由温度变换再生到由压力变换再生所预期的转变位置。在本发明的优选实施方案中，还按照进料气体水含量的函数进行再生热量的调节。
附图简述
图1是本发明一个实施方案的附图。
发明详述
参照图1，本发明涉及一种用于从进料气体(12)中除去水及CO2的吸附工艺，其中：
(a)该工艺采用具有用于引入进料气体的进料口(16)以及用于排出产品气体(20)的产品口(18)的吸附容器(14)；
(b)在进料口邻近处设置含有用于从进料气体中吸附水的水选择性吸附剂的水除去区(22)；
(c)在水除去区与产品口之间设置含有用于从进料气体中吸附CO2的CO2选择性吸附剂的CO2除去区(24)；
(d)该工艺在吸附工序与再生工序之间循环；
(e)在吸附工序中：
(i)进料气体从进料口开始流经该容器；
(ii)至少一部分水选择性吸附剂用水饱和；
(iii)至少一部分CO2选择性吸附剂用CO2饱和；且
(iv)产品气体从产品口排出；
(f)在再生工序中：
(i)将容器减压至较低(lower)压力；
(ii)加热的再生气体从产品口开始流经该容器，提供一些再生热以解吸基本上全部在吸附工序中吸附的CO2和部分在吸附工序中吸附的水；且
(iii)冷却的再生气体从产品口开始流经该容器，以解吸大部分或基本上全部在吸附工序中吸附的残留水份；且
(iv)用进料气体增压该容器使之为下一个吸附工序作好准备；且
(g)水除去区内所含有的水选择性吸附剂由等厚的十层组成，层1始于与进料气体口相邻的水除去区的一端，依次到层10，层10位于与CO2除去区相邻的水除去区的一端；
更具体而言，本发明是对上述工艺的改进，包括调节在(f)(ii)中提及的作为取自水选择性吸附区的关键部位的温度数据的函数的再生热量，如前面所述，该关键部位相当于热脉冲失效的设计位置，一般包含层2到9之间含端值的任何3-4个连续层，而更为通常的是包括层6到层9，由图1中水除去区的十字形阴影部分示出。
本发明的另一实施方案中，温度数据是从关键部位的两个位置获得的，即从层9中的位置和层6中的位置获得。
本发明的另一实施方案中，还调节作为进料气体水含量函数的、由被加热的再生气体所提供的热量(即：Kalbassi中所教导的)。
本发明的另一实施方案中，进料气体是空气。
本发明的另一实施方案中，将产品气体送入低温空气分离单元，并将其分离成其组成组分。
本发明的另一实施方案中，水选择性吸附剂是活性氧化铝。
本发明的另一实施方案中，水选择性吸附剂是硅胶。
本发明的另一实施方案中，CO2选择性吸附剂是分子筛。
本发明的另一实施方案中，进料气体是天然气。
本发明的另一实施方案中，进料气体是包括一氧化碳及氢气的合成气。
示于图1中的本发明的实施方案，采用垂直流动容器(如Kalbassi所教导的)，其中，进料口(14)位于吸附容器的底部，且进料气体(10)在到达位于吸附容器的顶部的产品口(16)之前，向上流经吸附容器。或者，本发明可采用径向流动容器(如Bosquain所教导的)，其中，进料口将进料气体分布于吸附容器的外部，且进料气体在到达位于吸附容器外部的产品口前，径向流经吸附容器(如Kalbassi所述，首先通过水除去区，然后通过CO2除去区)。

Claims (13)

1、一种用于从进料气体中除去水及CO2的吸附工艺，其中：
(a)该工艺采用具有用于引入进料气体的进料口以及用于排出产品气体的产品口的吸附容器；
(b)位于邻近于进料口的是含有用于从进料气体中吸附水的水选择性吸附剂的水除去区；
(c)位于水除去区与产品口之间的是含有用于从进料气体中吸附CO2的CO2选择性吸附剂的CO2除去区；
(d)该工艺在吸附工序与再生工序之间循环；
(e)在吸附工序中：
(i)进料气体从进料口开始流经该容器；
(ii)至少一部分水选择性吸附剂用水饱和；
(iii)至少一部分CO2选择性吸附剂用CO2饱和；且
(iv)产品气体从产品口排出；
(f)在再生工序中：
(i)将容器减压至较低压力；
(ii)加热的再生气体从产品口开始流经该容器，提供一些再生热以解吸基本上全部在吸附工序中吸附的CO2和部分在吸附工序中吸附的水；且
(iii)冷却的再生气体从产品口开始流经该容器，以解吸大部分或基本上全部在吸附工序中吸附的残留水份；
(iv)用进料气体增压该容器使之为下一个吸附工序作好准备；且
(g)水除去区内所含有的水选择性吸附剂由等厚的十层组成，层1始于与进料气体口相邻的水除去区的一端，依次到层10，层10位于与CO2除去区相邻的水除去区的一端；
其改进之处包括对作为取自水选择性吸附区的关键部位的温度数据函数的再生热量进行调节，该关键部位包含层2到9之间(并包括)含端值的任何3-4个连续层。
2、权利要求1所述的工艺，其中，水选择性吸附区的关键部位包含层6到9。
3、权利要求2所述的工艺，其中，温度数据是从关键部位的两个位置获得的，即从层9中的位置和层6中的位置获得。
4、权利要求1所述的工艺，其中，还调节作为进料气体水含量函数的由被加热的再生气体所提供的热量。
5、权利要求1所述的工艺，其中，进料气体是空气。
6、权利要求1所述的工艺，其中，将产品气体送入低温空气分离单元，并将其分离成其组成组分。
7、权利要求1所述的工艺，其中，水选择性吸附剂是活性氧化铝。
8、权利要求1所述的工艺，其中，水选择性吸附剂是硅胶。
9、权利要求1所述的工艺，其中，CO2选择性吸附剂是分子筛。
10、权利要求1所述的工艺，其中，进料气体是天然气。
11、权利要求1所述的工艺，其中，进料气体是包含一氧化碳及氢气的合成气。
12、权利要求1所述的工艺，其中，吸附容器是垂直流动容器，进料口位于吸附容器的底部，且进料气体在到达位于吸附容器的顶部的产品口之前，向上流经吸附容器。
13、权利要求1所述的工艺，其中，吸附容器是径向流动容器，进料口将进料气体分布于吸附容器的外部，且进料气体在到达位于吸附容器外部的产品口之前，径向流经吸附容器。
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SG126836A1 (en) 2006-11-29
IL174739A0 (en) 2006-08-20
ES2371926T3 (es) 2012-01-11
KR100777998B1 (ko) 2007-11-28
ATE523234T1 (de) 2011-09-15
US20060225569A1 (en) 2006-10-12
KR20060107320A (ko) 2006-10-13
ZA200602789B (en) 2008-04-30
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US7413595B2 (en) 2008-08-19
TW200640562A (en) 2006-12-01

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