CN1132659A - 从燃气中除去二氧化碳与氧化氮的方法 - Google Patents

从燃气中除去二氧化碳与氧化氮的方法 Download PDF

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CN1132659A
CN1132659A CN95120036A CN95120036A CN1132659A CN 1132659 A CN1132659 A CN 1132659A CN 95120036 A CN95120036 A CN 95120036A CN 95120036 A CN95120036 A CN 95120036A CN 1132659 A CN1132659 A CN 1132659A
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三村富雄
下条繁
饭岛正树
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Abstract

一种从燃气中一同除去CO2和NOx的方法,包括,首先,将燃气冷却到50-100℃,加入臭氧使燃气中的NO氧化成NO2。然后,在除CO2步骤中使气体与含醇式羟基的仲胺或叔胺的水溶液相接触,从而使NO2从燃气中与CO2一同除去。

Description

从燃气中除去二氧化碳与氧化氮的方法
本发明涉及从燃气中除去二氧化碳(CO2)与氧化氮(NOx)的方法。更具体地说,涉及用臭氧氧化将燃气中NOx的主要成分一氧化氮(NO)转化为二氧化氮(NO2)并通过吸收从燃气中一同除去NO2和CO2的方法。
目前,普遍认为矿物燃料的燃烧产生的CO2的温室效应会导致全球性温度升高,而其它燃烧产物NOx会导致光化烟雾和酸雨。尤其是酸雨已危及自然生态系统,直接作用于森林及农作物、通过改变土壤而间接影响到植被、由于酸化湖泊与河流而降低了鱼的数量。由于空气污染物CO2与NOx对环境的跨国界性的广泛危害,致使其成为极为紧迫的问题。
已采取一种方法,通过与单乙醇胺(MEA)、受阻胺等的水溶液相接触而从燃气(例如,大量燃烧矿物燃料的热电站锅炉所产生的燃气)中回收并除去CO2
另一方面,燃气的湿式脱硝技术进展困难,这是由于NOx浓度低,并且90%以上的NOx是活性差的NO。对于干式脱硝法,已使用的一种方法是通过催化剂的协助和氨的注入来降低燃气中的NOx。典型的湿式脱硝法为氧化吸收法,其要点是用水或化学试剂的溶液洗涤载有NOx的气体,用氧化剂等将NO氧化成NO2而有效地除去NO,然后用氧化剂溶液洗涤或直接冲洗。
上述湿式脱硝法的缺点是适用于吸收NOx的氧化剂成本高,并且需要排放用过的吸收液。燃气中通常含有约10%的CO2,但其NOx的含量至多为百万分之几百份,而增加专门脱硝步骤需要大规模的设备。对于同时除去CO2和NOx来说,还没有能将二者一同除去的令人满意的吸收剂。
因此,由于燃气对环境的影响,非常需要一种尽快解决现有技术问题的方法,该方法应操作简便、可以高效率同时回收CO2和NOx、并能引入现有燃气处理设备中。
为了解决上述问题,我们的研究结果表明,可通过首先用臭氧将NOx氧化成NO2并用某种除CO2的吸收剂将形成的NO2与CO2一同除去,进而从燃气中除去CO2和NOx。该发现导致了本发明。
本发明因此提供了一种从燃气中一同除去CO2和NOx的方法,其特征在于包括下列步骤:将燃气冷却至50-100℃,加入臭氧使气体中的NO氧化成NO2,使气体与含醇式羟基的仲胺或叔胺的水溶液相接触并从气体中一同除去NO2和CO2
按照本发明,首先在燃气处理等类似步骤中用臭氧将燃气中NOx的主要成分惰性NO氧化成NO2。然后,使气体与作为CO2吸收剂的含醇式羟基的仲胺或叔胺的水溶液相接触,从而一同除去CO2和NO2并得以回收。对于燃气中存在100ppmNOx来说,约90%为NO,如果臭氧氧化产生的NO2的化合量约为90%,气体中初始NO2含量将被除去,那么处理后气体中的NOx含量将降至仅为10ppm或更少。
下面将更详细地介绍从燃气中除去CO2和NOx的本发明方法。
按照本发明,在除去CO2和NOx的过程中最好能将燃气冷却并同时除尘。优选通过与冷却水直接接触而冷却到燃气中所含NOx的最佳氧化温度。就臭氧对NOx的反应活性来说,适宜的冷却温度范围为50-100℃,优选60-80℃。对于除尘来说,燃气除尘程度应与通常的湿式烟道气脱硝设备的除尘程度相同。
在用含臭氧(由臭氧发生器提供)的空气进行氧化的步骤中,已冷却的燃气内所含NOx中的NO轻易地被氧化成NO2。在实际的氧化步骤中,可向通过燃气的管路中通入臭氧。通常,燃气中NOx的浓度较低,活性差的NO占其中的90%以上,因此NOx大多被臭氧氧化成NO2。加入臭氧的量通常为NO含量的摩尔数的一倍。加入该计量的臭氧会使反应后含臭氧的燃气中不含过量臭氧。在臭氧与燃气混合很差的地方,臭氧与NOx间的反应可生成少量N2O5。为避免这种情况,建议适当安放向燃气导管中喷入臭氧的喷头,确使臭氧在气体中均匀分布。
在吸收步骤中,将CO2及用臭氧氧化产生的NO2与吸收液(含醇式羟基的仲胺或叔胺的水溶液)相接触,经吸收将二者除去。
作为CO2及NO2吸收液的含醇式羟基的仲胺水溶液是,例如,含一个羟基的胺,如2-(甲氨基)乙醇(MAE)、2-(乙氨基)乙醇〔EAE〕、2-(异丙基氨基)乙醇(IPAE)、N-(正丁基)乙醇胺、或N-(叔丁基)乙醇胺;或含有两个羟基的胺,如二乙醇胺。含醇式羟基的叔胺的水溶液的例子是含一个或两个羟基的叔胺,如2-(二甲氨基)乙醇、2-(二乙氨基)乙醇(DEAE)、(N-甲基)二乙醇胺(MDEA)、(叔丁基)二乙醇胺、三异丙醇胺、3-(N,N-二甲氨基)-1-丙醇,4-(N,N-二甲氨基)-1-丁醇、2-(N,N-二甲氨基)-2-甲基-1-丙醇、和3-(N,N-二甲氨基)-2,2-二甲基-1-丙醇。可将这些化合物中的两种或多种混合使用,或作为与促进CO2与NO2吸收的化合物(例如哌嗪)的混合物使用。
图1为体现本发明的方法的流程图。
图2为根据本发明的流程图图1中除去CO2和NOx步骤的示意图。
图3为显示实施例9中进行的湿壁实验结果的曲线图。
图1显示了体现本发明的燃气处理方法的流程图。符号A代表锅炉,B为冷却塔,C为臭氧发生器、D为氧化步骤、E为脱硫步骤、F为除去CO2与NO2的步骤、以及G为烟囱。
下面,通过参照图2来描述根据本发明流程图图1中的除CO2与NO2步骤F。显示了主要设备部件,但省去了小的辅助设备。除非另外指明,此处所说的“CO2”是指其中含有部分NO2
参见图2,显示了CO2-清除塔201,下层填料区202,上层填料区或塔板203,CO2-清除塔的燃气入口204,塔的燃气出口205,含醇式羟基的仲胺或叔胺的水溶液(此后称之为“吸收液”)入口206,数排喷头207,燃气冷却器208(当燃气进料温度足够低时可以省去),喷头209,填料区210,润湿—冷却水循环泵211,补给水进料管212,吸收液排放泵213,换热器214,吸收剂再生塔215(为简便起见也可称之为“再生塔”,喷头216,下层填料区217,再生加热器(再沸器)218,上层填料区219,回流水泵220,CO2分离器221,所回收的CO2的排出线路222,再生塔回流冷凝器223,喷头224,再生塔回流水进料管225,燃气鼓风机226,以及冷却器227。
在图2的操作中,用燃气鼓风机226将燃气压入燃气冷却器208。然后,在填料区210与从喷头209喷出的润湿—冷却水相接触并被湿润和冷却。然后,使气体经燃气入口204进入CO2-清除塔201。在燃气冷却器208的下部收集与燃气接触后的润湿—冷却水,并经润湿—冷却水循环泵211循环至喷头209。润湿—冷却水在润湿和冷却燃气的同时逐渐消耗,并由供给源通过补给水进料管212得以补充。
压入CO2-清除塔201的燃气通过下层填料区202逆流而上,与从喷头207以给定浓度喷出的吸收液相接触。在此期间,含醇式羟基的仲胺或叔胺的水溶液吸收除去了燃气中的CO2,脱去CO2的燃气继续上升进入上层填料区203。供给CO2-清除塔201的吸收剂从而吸收了CO2,并由于吸收的反应热使吸收剂比吸收剂入口处206变热。用吸收剂排液泵213将吸收剂输送到换热器214,吸收剂在其中再加热并输送到再生塔215。
在再生塔215中,吸收剂经再沸器(再生加热器)218加热再生,被换热器214冷却,如需要可经冷却器227冷却,再回到CO2-清除塔201的上部。从吸收剂中分离出来的CO2与从再生塔215上部的喷头224中喷出的回流水相接触,并经再生塔回流冷凝器223冷却。然后,在CO2分离器221中从回流水中分离出CO2,也就是将夹带CO2的水蒸汽冷凝成水,并通过所回收的CO2的排出线路222排到CO2清除站。部分回流水经回流水泵220返回到再生塔215,同时,其余部分经再生塔回流水进料管225循环到CO2-清除塔201的上部。
在本发明的实际操作中,当欲处理的燃气中SOx含量足够大时可在除CO2步骤前进行脱硫步骤。在这种情况下,脱硫后的燃气在除CO2步骤中进一步得以处理,从而可将SOx与CO2和NO2一同几乎完全除去。这是由于除CO2步骤中所用的含醇式羟基的仲胺或叔胺的水溶液也与SOx反应。当燃气中SOx含量很低不适宜用脱硫步骤时,SOx可在CO2-清除塔中与CO2和NO2一样几乎完全除去。
下面将结合表1和图3来讨论本发明的实施例。
实施例1-8及比较实施例1-4
首先解释实施例1-8。向放置在恒温箱中的每个玻璃反应容器中分别加入50ml表1中所列的各种吸收液或含醇式羟基的仲胺或叔胺水溶液。在40℃搅拌下使测试气于常压下以每分钟一升的流量通过吸收液,通过滤器以便轻易地形成气泡。测试气为模拟燃气,其在40℃时的组成为10摩尔%CO2,约10ppmNO2,及90%N2。使测试气连续通过吸收剂直至进入与输出气流中CO2浓度相等,用CO2分析仪(总有机碳测定仪)测定吸收液中CO2的含量,并确认吸收已饱和。还测定了出口处NO2的最初浓度,或测定吸收实验的初始阶段反应容器出口处气体中的NO2浓度。可以有把握地说,出口处NO2的最初浓度越低,吸收剂对NO2的吸收率就越高。
通过比较实施例,还进行了表1中所列的伯胺水溶液的吸收实验。表1中列出了NO2的饱和吸收及所获得的出口处NO2的最初浓度值。
从表1中可以发现,如实施例1至8中所示,与比较实施例相比,使用根据本发明的含醇式羟基的仲胺或叔胺水溶液降低了出口处NO2的最初浓度。
所有用过的吸收液可经加热很容易地得以再生。
                            表1
        吸收液               NO2吸收数据
 胺化合物     浓度,重量% 进口处NO2浓度,ppm 出口处NO2浓度,ppm 初始的吸收率,%
比较实施例1234  MEAMEAAMPAMP+P     304030303     10111111     101087     09.127.336.4
实施例1234  EAEEAEMAEIPAE     30403030     10101011     5655     50.040.054.550.0
实施例5678  MDEAMDEA+PDEAEDEAE+P     3030330303     11101011     4434     63.660.070.063.6
P=哌嗪    MEA=单乙醇胺    AMP=腺苷酸
实施例9
作为实施例9,用湿壁式吸收设备作为图2中所示的除CO2流程的主要装置进行接触吸收实验,使用调节到给定CO2及NO2浓度的测试气,用EAE水溶液作为吸收剂。为了进行比较,还用MEA水溶液作为吸收剂进行了接触吸收实验。结果示于图3。
使用的与其它实验相同的测试条件如下。进料气体中的CO2与O2浓度设定为锅炉燃气的平均值。
〔相同条件〕CO2吸收塔的类型:     湿壁式吸收塔塔的内径及高度:       15mm直径×7500mm气体中的CO2浓度:     10体积%气体中的O2浓度:      2体积%进气温度:             60℃进气量:               2m3N/h吸收液浓度:           30重量%吸收液用量:           4升/小时
如上所述,本发明的方法通过用臭氧氧化气体而将气体中的NOx转化为NO2,在其除CO2步骤中从燃气中除去了CO2和NOx

Claims (3)

1.一种从燃气中一同除去CO2和NOx的方法,该方法包括下列步骤:将燃气冷却到50-100℃,向燃气中加入臭氧使燃气中的NO氧化成NO2,然后,使气体与含醇式羟基的仲胺或叔胺的水溶液相接触,从而从燃气中除去NO2和CO2
2.根据权利要求1的方法,其中的燃气为燃烧矿物燃料产生的废气。
3.根据权利要求1的方法,其中的臭氧为含有由臭氧发生器提供的臭氧的空气。
CN95120036A 1994-12-15 1995-12-01 从燃气中除去二氧化碳与氧化氮的方法 Expired - Fee Related CN1069222C (zh)

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