CN1186428C - 换热式焦炉煤气加压催化部分氧化法制取合成气的工艺 - Google Patents
换热式焦炉煤气加压催化部分氧化法制取合成气的工艺 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
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Abstract
本发明属于焦炉煤气制取合成气的一种方法，如制取甲醇或合成氨的合成气。采用了两台换热式的预热器，充分利用了转化炉出来的转化气的废热。在转化炉上部设置了燃烧空间，设定了镍催化剂床层的最低温度，指明了蒸汽压力与氧气(或富氧空气)压力的关系，制定了防止焦炉煤气窜入到氧气(或富氧空气)管道的方法，从而在焦炉煤气催化部分氧化领域达到了节能、节省投资、安全运行的目的。
Description
本发明属于化工领域焦炉煤气制取合成气的一种方法，合成气主要是指合成甲醇合成氨以及凡在合成反应中以氢气、一氧化碳和二氧化碳为合成反应有效成份的原料气。
焦炉煤气的成份按体积百分数计，主要是H2(约占53～59％)、CH4(约占25～30％)，其次是CO(6％左右)、CO2(2.5％左右)、N2(4％左右)、O2(0.5％左右)、CmHn(2.5％左右)。制取合成氨的合成气必须是H2和N2，制取合成甲醇的合成气是H2和CO(也可配入少量CO2)。焦炉煤气的转化实质就是将煤气中的烃(主要是CH4)转化为H2及CO，以制得上述的合成气。
CH4在有足够热量供应以及有镍催化剂存在条件下，与H2O蒸汽或CO2反应，均可制取H2+CO，这是一个吸热反应，由于提供热量的方法不同，焦炉煤气的转化有蒸汽转化和部分氧化之分，蒸汽转化是指由外部燃料燃烧提供热量经过反应器的金属壁传热进行上述反应，烟道气则排人大气中。部分氧化是指焦炉煤气中有部分气体(主要是H2)在转化炉内与纯氧(或富氧空气)进行燃烧反应，直接为上述吸热反应提供热量，即先燃烧反应再进行上述吸热转化的反应都在同一设备(转化炉)内部完成。
本发明属于部分氧化，制取合成气的原料气是三种，即焦炉煤气、水蒸汽和氧化剂。对于制取合成氨来说，氧化剂是富氧空气，含O236％左右，以便补充合成氨所需N2气。对于合成甲醇来说，由于不需要N2，所以氧化剂是纯氧即氧气。
本发明的目的，是通过一种新的工艺设计，使本发明比常规的甲烷蒸汽转化法更节能，而且在甲烷部分氧化法制取合成气的转化领域更具有节约原料、节省投资、安全运行及保护镍催化剂的领先优势。
本发明为换热式加压催化部分氧化工艺，现将这一工艺说明如下：
从炼焦厂来的已除去绝大部分杂质的焦炉煤气经压缩机压到2.07MPa(表压，下同)首先进入有旁通调温管道的焦炉煤气初预热器1，与焦炉煤气-蒸汽预热器2来的转化气换热，从常温升到300℃，再去含有铁钼催化剂的干法脱硫装置5，在这一装置里，焦炉煤气中少量的烯烃转化为CH4，有机硫和无机硫被脱除。然后洁净的焦炉煤气与转化气废热锅炉中来的2.4MPa的蒸汽混合，进入有旁通调温管道的焦炉煤气-蒸汽预热器2中，与废热锅炉4来的转化气换热，反温度提高到500℃后，经转化炉3的炉头3a与纯氧(或富氧空气)混合向下进入转化炉3的燃烧空间3b，在燃烧空间3b里，O2与焦炉煤气中的H2进行燃烧反应：
另外还有CH4、CO的燃烧反应。但由于H2的燃烧反应比其它燃烧反应快1000倍以上，所以在燃烧空间3b里，主要进行H2的燃烧反应，燃烧空间的温度在1050～1150℃左右。
在燃烧空间3b里，氢的燃烧为转化炉3的镍催化剂床层3c的CH4转化提供了足够的热量：
催化剂床层的温度一般稍高于950℃，从安全上讲，不能低于710℃。此转化反应后的气体已无O2，主要是H2、CO、CO2和过量水蒸汽(如果用富氧空气而不是用纯氧作氧化剂，则还含有N2，作为合成氨的原料N2使用)。
转化炉出口最终的反应平衡和组成是由下述CO的变换反应决定的：
转化炉出口转化气中的CH4含量将降至0.4％(体积)。
焦炉煤气的部分氧化可分为燃烧空间的氧化放热反应及镍催化剂床层的吸热转化反应两个阶段，转化炉3中的热电偶3d可以检测出燃烧空间的温度在1050～1150℃，而催化剂层主要进行CH4的吸热转化反应，温度约950～980℃，明显低于燃烧空间。
由于进转化炉的焦炉煤气已没有易折碳的烯烃，所以在转化炉3的炉头3a各气体混合均匀的情况下，只要水蒸汽的加入量大于CH4析碳的最小H2O/CH4比，是完全可以防止析碳的。
从转化炉3出来的转化气经废热锅炉4产生蒸汽降温后，再依次经焦炉煤气-蒸汽预热器和焦炉煤气初预热器降温至350℃，成为合成甲醇(或合成氨)的合成气，送出本系统。
送人转化炉的氧气(或富氧空气)可以常温或经过预热炉加热后直接进入转化炉的炉头内混合器3a，氧气进入转化炉的压力在2.1MPa，为了防止炉头3a的焦炉煤气窜流入氧气管道，在氧气管道上的止回阀6与转化炉3之间接通一根蒸汽管，使少量的压力高于氧气(或富氧空气)的水蒸汽能连续通过氧气(或富氧空气)管道进入转化炉。换热式焦炉煤气加压催化部分氧化法制取合成气的工艺流程图见说明书附图。
Claims (1)
1、一种换热式焦炉煤气加压催化部分氧化法制取合成气的工艺，其特征在于：所述的工艺步骤为：
第一步：含CH4 25-30％的焦炉煤气在常温及2.07Mpa压力下经焦炉煤气初预热器加热到300℃后，再通过干法脱硫装置与废热锅炉来的2.4Mpa压力的饱和蒸气混合，进入焦炉煤气-蒸汽预热器进一步加热到500℃，并于1.8Mpa压力下进入转化炉炉头，与纯氧或富氧空气经过止回阀和少量的密封蒸汽混合后，在2.1Mpa压力下也送入转化炉炉头；
第二步：焦炉煤气与蒸汽的混合气在炉头内再与纯氧或富氧空气混合向下流动，在转化炉的催化剂层里进行转化反应，当氧化剂是纯氧时，反应产物是甲醇合成气，当氧化剂是含氧36％的富氧空气时，反应产物是氨合成气；
第三步：从转化炉出来的合成气960℃，CH4含量0.4％，此合成气经废热锅炉、焦炉煤气-蒸汽预热器、焦炉煤气初预热器逐级降温到350℃后送出。
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| CN1186428C true CN1186428C (zh) | 2005-01-26 |
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| CN100586840C (zh) * | 2006-12-07 | 2010-02-03 | 浙江大学 | 焦炉煤气吸附强化的催化反应制氢方法及其装置 |
| CN102634369A (zh) * | 2012-04-17 | 2012-08-15 | 焦云 | 高温煤焦油加氢、后延迟焦化与焦炉煤气制甲醇组合工艺 |
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