CN103582610A - 向合成气制造装置中的金属混入抑制方法 - Google Patents
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Abstract
本发明防止向GTL(Gas-To-Liquid)工艺的合成气制造工序中使用的合成气制造装置(重整装置)中的金属成分的混入。向合成气制造装置中的金属混入抑制方法,是包括使天然气和包含蒸汽和/或二氧化碳的气体在合成气制造装置内进行重整反应制造合成气的合成气制造工序的GTL工艺的合成气制造装置中的金属混入抑制方法,其特征在于,将该合成气制造工序中制造的该合成气中的二氧化碳分离回收,将分离回收的该二氧化碳再循环到该合成气制造工序中的重整反应的原料气时,该再循环的二氧化碳中含有的镍的浓度为0.05ppmv以下。
Description
技术领域
本发明涉及向合成气制造装置中的金属混入抑制方法。特别地,本发明涉及防止向GTL(Gas-To-Liquid)工艺的合成气制造工序中的合成气制造装置中的镍成分的混入的方法。
背景技术
石油资源的未来的枯竭危机已久。这段期间,为了少量降低对石油资源的依存度,进行了使天然气、煤或生物质这样的其他的碳源为原料,制造石脑油、灯轻油等各种烃油的技术的研究。其中,GTL工艺作为技术可以说达到了基本实用化的水平,在富产天然气的地区,实用的规模的成套设备已开始运转。而且,状况是同样的成套设备今后也会进一步进行建设。
GTL工艺是通过将以甲烷(CH4)作为主成分的天然气重整,制造以氢(H2)和一氧化碳(CO)作为主成分的合成气,以该合成气作为原料,进行费-托(Fischer-Tropsch)合成(FT合成),从而制造作为包含重质烃的各种烃油的混合物的所谓费-托油(FT油),通过将得到的FT油改质(Upgrading)精制,从而制造石脑油、灯油、轻油等各种石油制品。这样,GTL工艺大致由合成气制造工序(重整工序)、费-托油制造工序(FT工序)和改质工序(UG工序)这3个工序组成。
对于合成气的制造,首先,将作为原料的天然气中含有的硫化合物在脱硫装置中脱硫。然后,在经脱硫的天然气中添加蒸汽和/或二氧化碳后,导入合成气制造装置(以下也称为“重整装置”)加热,从而利用重整装置内填充的重整催化剂的催化剂作用进行重整反应,制造合成气。作为重整反应,主要采用使用蒸汽的水蒸气重整法,近年来,采用二氧化碳的二氧化碳重整法也已实用化。如果采用二氧化碳重整法,不必将天然气中含有的二氧化碳在重整反应前分离除去,因此具有实现合成气制造工序的效率化、低成本化的优点。此外,能够将制造的合成气中含有的未反应二氧化碳、生成二氧化碳分离回收,再循环到合成气的制造工序,再利用于二氧化碳重整法,因此实现二氧化碳的进一步的资源化。
在合成气制造工序中,将天然气重整生成的合成气中含有的二氧化碳采用化学吸收法在二氧化碳分离回收装置分离回收后,将该二氧化碳作为天然气重整的原料气,再循环到合成气制造装置。采用化学吸收法将二氧化碳分离回收的工序中,在二氧化碳分离回收装置中贮存的吸收液吸收二氧化碳。通常,在二氧化碳分离回收装置的吸收塔、再生塔的填充材料中使用了含镍的不锈钢材料。此外,通常,作为吸收液,使用含伯胺的水溶液。但是,本发明人发现,取决于将二氧化碳分离回收的条件,吸收了二氧化碳的伯胺水溶液引起作为二氧化碳分离回收装置的填充材料的含有镍的不锈钢材料的腐蚀。由于在合成气中含一氧化碳,因此因腐蚀而溶解的镍成分、二氧化碳分离回收装置的填充材料与一氧化碳反应,生成羰基镍。
这样,在二氧化碳分离回收装置内生成的羰基镍与作为使天然气重整的原料气再循环的二氧化碳一起被供给到重整装置。然后,供给到重整装置的羰基镍附着于在重整装置内填充的重整催化剂上,使作为重整反应的副反应的碳析出·堆积。其结果,担心使重整催化剂的催化剂活性降低。此外,也担心羰基镍分解,在设置于再循环管线的压缩机等旋转设备、热交换器作为镍金属附着,这样的设备不能长期稳定运转。
现有技术文献
专利文献
专利文献1:特开2001-342003
发明内容
发明要解决的课题
本发明的目的在于尽可能抑制从二氧化碳分离回收工序向合成气制造工序再循环的二氧化碳中所含的羰基镍,防止由于在合成气制造工序的重整装置内镍促进碳生成反应而使重整催化剂中毒。
用于解决课题的手段
本发明通过提供如下的向合成气制造装置中的金属混入抑制方法,从而解决上述课题,其为包括使天然气和包含蒸汽和/或二氧化碳的气体在合成气制造装置内重整反应制造合成气的合成气制造工序、使该合成气制造工序中制造的合成气费-托反应后从费-托反应生成物分离气体状生成物制造费-托油的费-托油制造工序和对该费-托油制造工序中制造的费-托油进行氢化处理和蒸馏而制造各种烃油的改质工序的GTL(Gas-to-liquid)工艺的合成气制造装置中的金属混入抑制方法,其特征在于,将该合成气制造工序中制造的该合成气中的二氧化碳分离回收,将分离回收的该二氧化碳再循环到该合成气制造工序中的重整反应的原料气时,该再循环的二氧化碳中含有的镍的浓度为0.05ppmv以下。
发明的效果
根据本发明,由于尽可能地抑制向GTL工艺的合成气制造工序的重整装置再循环的二氧化碳中所含的羰基镍浓度,因此能够抑制(防止)在重整装置内填充的合成气制造用重整催化剂的表面的碳析出·堆积,能够防止重整催化剂的催化剂活性的降低。此外,具有抑制(防止)在合成气制造工序内的设备,例如压缩机、热交换器的镍的附着,这样的设备能够长期稳定运转的优点。
附图说明
图1表示本发明涉及的GTL工艺的第1实施方式中的合成气制造工序的工艺流程。
图2表示本发明涉及的GTL工艺的第2实施方式中的合成气制造工序的工艺流程。
具体实施方式
以下对本发明的实施方式具体地说明。不过,本发明并不受以下的实施方式限定。
图1表示本发明涉及的GTL工艺的实施方式中的合成气制造工序的工艺流程。再有,图1并不是表示该合成气制造工序的工艺流程的全部,主要表示与合成气制造工序内的CO2的流通有关的主要流程。因此,例如,应注意没有示出将在合成气制造工序制造的合成气中所含的蒸汽分离的流程等。
图1中,合成气制造工序主要由具备脱硫装置1的脱硫工序、合成气制造装置2和具备脱碳酸装置5的脱碳酸工序组成。脱硫装置1将天然气中所含的硫成分除去。合成气制造装置2使从脱硫装置1导入的天然气与包含蒸汽和/或二氧化碳的气体进行重整反应,制造合成气。所谓重整反应,是指使天然气与蒸汽和/或二氧化碳反应,生成主要由氢和一氧化碳组成的合成气的反应。
导入合成气制造工序的气体,将来自作为原料的烃的碳摩尔数用C表示时,以作为每1摩尔碳的蒸汽(H2O)的比的H2O/C摩尔比成为0.1~3.0和/或作为每1摩尔碳的二氧化碳(CO2)的比的CO2/C摩尔比成为0.1~3.0,优选地H2O/C摩尔比成为0.3~2.0和/或CO2/C摩尔比成为0.3~1.0的方式添加蒸汽和/或二氧化碳。
其中,所谓水蒸气重整法,是在天然气中添加蒸汽,按照以下的反应式(1)生成合成气,所谓二氧化碳重整法,是在天然气中添加二氧化碳或者使用天然气中含有的二氧化碳,按照以下的反应式(2)生成合成气。再有,在下述的式中,以天然气中主要含有的甲烷的重整反应为例表示。
式(1):CH4+H2O→CO+3H2
式(2):CH4+CO2→2CO+2H2
本实施方式中,能够同时进行水蒸气重整法和二氧化碳重整法,调整生成的CO和H2的比率。本发明的费-托反应中接近作为优选的比率的H2/CO=2.0成为可能,节省其后的调整的麻烦,因此优选。
在合成气制造装置2内,配置着填充有促进上述重整反应的重整催化剂的多个反应管。作为重整催化剂,优选使用在碱土类金属氧化物载体上负载VIII族金属等催化剂金属的催化剂。通过向合成气制造装置2供给燃料(通常为天然气)和空气,燃烧器燃烧,将配置在合成气制造装置2内的反应管群从外部加热。将反应管群在合成气制造装置2内加热,在反应管内流通的天然气和包含蒸汽和/或二氧化碳的气体在重整催化剂的存在下进行重整反应,生成由氢和一氧化碳组成的合成气。
在合成气制造装置2的反应管群制造的合成气被废热锅炉3和合成气冷却器4冷却后,被导入脱碳酸装置5的二氧化碳吸收塔6。脱碳酸装置5具备二氧化碳吸收塔6和再生塔7,将在合成气制造装置2制造的合成气中含有的二氧化碳分离回收。二氧化碳吸收塔6,利用二氧化碳吸收塔6内贮存的胺系的吸收液,将从合成气冷却器4供给的合成气中的二氧化碳吸收。
利用胺水溶液的二氧化碳吸收反应按照以下的反应式(3),作为碳酸氢离子吸收。
式(3):R-NH2+CO2+H2O→R-NH3 ++HCO3 -
将吸收了二氧化碳的吸收液导入再生塔7。再生塔7,通过将从二氧化碳吸收塔6供给的吸收液用蒸汽加热,进行汽提处理,通过式(3)的逆反应使二氧化碳放散,使吸收液再生。作为在吸收液中使用的胺类,能够使用包含一乙醇胺这样的伯胺、二甘醇胺这样的仲胺、甲基二乙醇胺(MDEA)这样的叔胺等的水溶液,优选使用包含叔胺,特别是金属材料的腐蚀性弱的MDEA的水溶液。这样,脱碳酸装置5将合成气中含有的二氧化碳分离回收。然后,将二氧化碳分离除去的合成气输送到FT工序。将去除了二氧化碳的吸收液再供给到二氧化碳吸收塔6,作为二氧化碳吸收塔6的吸收液再循环。
作为二氧化碳吸收塔6和再生塔7的填充物的材料,优选使用不含镍的材料。例如,优选将SUS410这样的不含镍的不锈钢、钛、陶瓷等单独或者2种以上组合使用。
将用脱碳酸装置5分离回收的二氧化碳从再生塔7导入合成气制造装置2,作为重整反应的原料气再利用。即,二氧化碳成分作为合成气制造工序内使天然气重整的物质再利用。
向合成气制造装置2再循环的用脱碳酸装置5分离回收的二氧化碳中所含的羰基镍的浓度以镍金属换算,优选为0.05ppmv以下。如果羰基镍的浓度以镍金属换算为0.05ppmv以上,使合成气重整催化剂的活性降低,因此不优选。
用脱碳酸装置5分离回收的二氧化碳中所含的羰基镍的浓度以镍金属换算为0.05ppmv以上时,如图2中所示,希望在从脱碳酸装置5到合成气制造装置2的二氧化碳再循环管线的途中设置羰基镍的吸附装置8,将二氧化碳中含有的羰基镍除去到0.05ppmv以下。作为羰基镍的吸附装置,优选使用填充了以活性炭作为主成分的吸附剂的装置。作为吸附装置中的操作条件,温度为250℃~400℃,压力为0.02~3.0MPaG,气体空间速度(GHSV)为500~3,000h-1。
使用以活性炭作为主成分的吸附剂,在上述操作条件下实施了羰基镍的吸附的情况下,由于羰基镍作为镍金属被分解吸附于活性炭上,因此能够长时间稳定地进行吸附操作。
用脱碳酸装置5分离回收的二氧化碳中含有的羰基镍的浓度,例如,将分离回收的二氧化碳的水分用氯化钙除去后,用三氯乙烯和干冰冷却的碘-乙醇溶液吸收羰基镍,能够用电感耦合等离子体质量分析计对得到的吸收液进行测定。
通过成为该构成,用脱碳酸装置5分离回收、向合成气制造装置2再循环的二氧化碳中的羰基镍浓度以镍金属换算计成为0.05ppmv以下,因此能够防止将镍导入合成气制造装置,能够避免合成气重整催化剂的劣化。
实施例
以下为了对本发明的进一步的理解,使用实施例进行说明,但这些实施例并不限定本发明。
[实施例1]
在天然气中添加蒸汽和二氧化碳以使H2O/C摩尔比成为1.1和CO2/C摩尔比成为0.4,向填充有在碱土类金属氧化物载体上负载了VIII族金属的重整催化剂的重整装置中,在入口温度500℃、出口温度880℃、压力2.0MPaG、GHSV3,000h-1的条件下导入,制造合成气。为了从得到的合成气(H2:58%、CO:28%、CO2:7%、CH4:7%)将CO2分离回收,向二氧化碳吸收塔6中在温度40℃、压力2MPaG的条件下导入。二氧化碳吸收塔6是填充有不含镍的不锈钢材料SUS410的阶梯环的填充塔形式的吸收塔,导入的合成气与含叔胺的MDEA的水溶液以向流气液接触,将二氧化碳吸收除去。使吸收了二氧化碳的吸收液与从再生塔7向二氧化碳吸收塔再循环的高温的吸收液热交换后,向填充有SUS410的填充物的再生塔7在温度100℃、压力0.1MPaG下导入,将吸收液中的二氧化碳汽提。将汽提的二氧化碳冷却到0.08MPaG、40℃。该回收的二氧化碳中的羰基镍浓度以镍金属换算计为0.04ppmv。
[比较例1]
为了从与实施例1相同的合成气制造工序中得到的合成气(H2:58%、CO:28%、CO2:7%、CH4:7%)将CO2分离回收,向二氧化碳吸收塔6中在温度40℃、压力2MPaG的条件下导入。二氧化碳吸收塔6填充有含有镍的不锈钢材料SUS304的阶梯环,使导入的合成气与含伯胺的一乙醇胺的水溶液以向流气液接触,将二氧化碳吸收除去。吸收了二氧化碳的吸收液与从再生塔7向二氧化碳吸收塔再循环的高温的吸收液热交换后,向填充有SUS304的填充物的再生塔7以温度100℃、压力0.1MPaG导入,将吸收液中的二氧化碳汽提。将汽提的二氧化碳冷却到0.08MPaG、40℃。该回收的二氧化碳中的羰基镍浓度以镍金属换算计为2.0ppmv。
[实施例2]
将比较例1中回收的二氧化碳(羰基镍浓度以镍金属换算计为2.0ppmv)升压到2.2MPaG后,升温到250℃,以GHSV1,500h-1的空间速度使其通过填充有羰基镍吸附材料(商品名:Actisorb400、ズードケミー触媒社制)的吸附装置,结果二氧化碳中的羰基镍浓度以镍金属换算计减少到0.02ppmv。
本申请要求于2011年3月31日申请的日本专利申请第2011-078808号的优先权,通过引用其内容而使其成为本申请的一部分。
附图标记的说明
1.脱硫装置
2.合成气制造装置
3.废热锅炉
4.合成气冷却器
5.脱碳酸装置
6.二氧化碳吸收塔
7.再生塔
8.吸附装置
Claims (5)
1.向合成气制造装置中的金属混入抑制方法,其特征在于,是向GTL(Gas-to-liquid)工艺的合成气制造装置中的金属混入抑制方法,该GTL工艺包括在合成气制造装置内使天然气和包含蒸汽和/或二氧化碳的气体进行重整反应而制造合成气的合成气制造工序、使该合成气制造工序中制造的合成气进行费-托反应后从费-托反应生成物分离气体状生成物制造费-托油的费-托油制造工序、和对该费-托油制造工序中制造的费-托油进行氢化处理和蒸馏而制造各种烃油的改质工序,
将该合成气制造工序中制造的该合成气中的二氧化碳分离回收,使分离回收的该二氧化碳再循环到该合成气制造工序中的重整反应的原料气时,该再循环的二氧化碳中所含的镍的浓度为0.05ppmv以下。
2.权利要求1所述的方法,其特征在于,上述合成气中的二氧化碳用含叔胺的水溶液分离回收。
3.权利要求1或2所述的方法,其特征在于,上述合成气中的二氧化碳用填充有由不含镍的材料制成的填充物的脱碳酸装置分离回收。
4.权利要求1~3的任一项所述的方法,其特征在于,将上述分离回收的二氧化碳在温度250℃~400℃、压力0.02~3.0MPaG、GHSV500~3,000h-1下导入具有以活性炭作为主成分的吸附剂的吸附装置后,导入上述合成气制造装置。
5.权利要求1~4的任一项所述的方法,其特征在于,供给到上述合成气制造装置的气体的H2O/C摩尔比为0.1~3.0和/或CO2/C摩尔比为0.1~3.0。
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2011
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CN111566188A (zh) * | 2017-11-15 | 2020-08-21 | 美国燃气技术研究院 | 用于将甲烷和轻质烃重整为液烃燃料的方法和系统 |
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AU2012235395B2 (en) | 2015-04-16 |
BR112013025187A2 (pt) | 2021-03-23 |
AP2013007174A0 (en) | 2013-10-31 |
CA2831561A1 (en) | 2012-10-04 |
BR112013025187B1 (pt) | 2022-03-03 |
EA201391434A1 (ru) | 2014-01-30 |
EA035192B1 (ru) | 2020-05-12 |
JP2012214529A (ja) | 2012-11-08 |
CA2831561C (en) | 2016-04-19 |
WO2012132337A1 (ja) | 2012-10-04 |
US9725656B2 (en) | 2017-08-08 |
JP5804747B2 (ja) | 2015-11-04 |
US20140018450A1 (en) | 2014-01-16 |
AP3483A (en) | 2015-12-31 |
EA201891476A1 (ru) | 2019-03-29 |
ZA201307218B (en) | 2014-06-25 |
EP2692690A4 (en) | 2014-08-27 |
EA031520B1 (ru) | 2019-01-31 |
US20160272895A1 (en) | 2016-09-22 |
BR112013025187B8 (pt) | 2022-08-02 |
US9884998B2 (en) | 2018-02-06 |
EP2692690A1 (en) | 2014-02-05 |
MY175361A (en) | 2020-06-22 |
AU2012235395A1 (en) | 2013-10-31 |
CN103582610B (zh) | 2017-07-04 |
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