CN107001036B - 一种通过烟气再循环生成合成气的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 33
- 239000007789 gas Substances 0.000 title claims abstract description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003546 flue gas Substances 0.000 title claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 230000006835 compression Effects 0.000 claims abstract description 8
- 238000007906 compression Methods 0.000 claims abstract description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 238000002407 reforming Methods 0.000 claims description 11
- 239000003345 natural gas Substances 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 210000002700 urine Anatomy 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种用于生成合成气的新方法，其包括在一段重整器(PR)中处理烃类进料，在压缩机(C1)中压缩来自一段重整器的烟气的至少一部分，并将该压缩的烟气与一段重整器流出物一起供应至二段重整器(SR)。在此方法中，将富集的空气(EA)添加至一段重整器或二段重整器或其二者。该方法特别适用于氨和甲醇的共同生产，或者氨和甲醇二者之一的生产。通过使用本发明的方法，总的CO2排放量显著降低。
Description
技术领域
本发明涉及一种通过烟气再循环生成合成气的方法。该方法特别适用于氨和甲醇的共同生产，或者氨和甲醇二者之一的生产。
更具体地，本发明基于如下事实：可通过将来自一段重整器的烟气再循环到作为氧化剂的二段重整器来显著降低在例如氨装置中的诸如天然气(NG)的烃原料气的消耗和来自所述装置的二氧化碳的排放。
根据本发明，也与烟气一起再循环的二氧化碳可用于甲醇的共同生产，这也将减少二氧化碳排放。有利地，为了提高氢/氮比，富集的空气可用作用于一段重整器燃烧器的燃烧空气。然而，可将富集的空气添加到二段重整器而不是添加到一段重整器，或者可将其同时添加到两个重整器。
背景技术
氨和甲醇的共同生产例如从归属于申请人的US 8,692,034中获悉。将CO2变压吸附(CO2PSA)尾气流连同从氨合成获得的尾气燃料流一起再循环至一段重整器。来自一段重整器的部分重整的气体在吹气式二次重整阶段被进一步重整，但未提及来自一段重整器的烟气的处理。在甲醇合成步骤之后，包括甲烷化步骤。没有发生CO2(从甲醇和氨的合成捕获的)排放到周围环境。
也归属于申请人的US 8,303,923描述了一种从烃类进料共同生产氨和甲醇的方法。将来自氨合成反应器的包含氢、氮和甲烷的尾气燃料返回到一次重整阶段，但未提及来自一段重整器并从一段重整器转移到二段重整器的烟气的任何处理。在用于转化碳氧化物的甲醇合成步骤之后包括甲烷化步骤，并且避免了水煤气变换(WGS)和CO2去除步骤。
由C.Song,W.Pan和S.T.Srimat在“使用没有CO2预分离的发电厂烟气中的CO2进行天然气三重整，用于生产具有期望的H2/CO比的合成气(Tri-reforming of Natural Gasusing CO2in Flue Gas of Power Plants without CO2-Pre-separation for Productionof Synthesis Gas with desired H2/CO Ratios)”，由Maroto-Valer等人编辑的二十一世纪化石燃料利用的环境挑战与温室气体控制(edited by Maroto-Valer et al.,Environmental Challenges and Greenhouse Gas Control for Fossil FuelUtilization in the 21st Century)，Kluwer Academic/Plenum Publishers，New York，2002年第18章中描述了称为三重整的过程性概念，其基本上是蒸汽重整和CO2重整的组合，其中CO2来源于烟气。该概念披露了控制CO2排放的新方法。这包括利用存在于烟气中的CO2连同O2、H2O和N2一起，而无需首先将其与烟气分离。通过进行三重整，可实现CO2转化为甲醇。三重整方法和本发明之间的主要差异包括以下事实：在三重整中，烟气中的氮气被认为是惰性的，未提及氨作为包括三重整的方法的产物，并且可商购的基于Ni的催化剂R67的使用是可预见的。
关于三重整方法，可相对于合成气的低压(需要压缩合成气流)、合成气中的高氮含量和重整器中的高体积流量来表达保留率。
发明内容
现在已经证明，可使用来自例如氨和甲醇共同生产的烟气，因为氮气是氨生产所需要的，并且CO2可用于增加碳流量，从而能实现甲醇和尿素生产。
氨和甲醇的共同生产或者氨和甲醇二者之一的生产是根据本发明的方法的两个优选实施方案。但是本发明不局限于此，其它可能的实施方案可以是氨和氢气的共同生产、甲醇和一氧化碳的共同生产以及氨、甲醇和尿素的共同生产。
附图说明
附图示出了用于进行根据本发明的方法的反应器设计。
发明详述
将由蒸汽和任选的预重整烃类的混合物组成的烃类进料(例如包括天然气(NG))连同燃料和空气一起供应至一段重整器(PR)。将富集的空气(EA)供应至一段重整器或者二段重整器(SR)或其两者。在压缩机(C1)中将来自一段重整器的烟气的至少一部分压缩，并连同一段重整器流出物一起进料到二段重整器(SR)，同时将过剩的烟气(如果有的话)燃烧。
如果例如仅生产氨和/或期望能够调节甲醇和氨之间的比例，则任选需要变换工段和旁路。
任选通过变换工段将来自二段重整器的流出物供应至CO2去除单元，其中可将用于尿素生产的CO2与流出物分离。如上所述，可将CO2去除单元设置旁路。无论是否通过CO2去除单元，都在压缩机(C2)中将流出物压缩，并且任选在甲醇合成单元(M)中进行甲醇生产，从甲醇合成单元(M)抽出粗甲醇。通过压缩机(C3)将剩余部分送至氨回路(AL)。
氨回路的上游必须进行合成气净化(s.c)。作为最低限度，必须例如通过甲烷化去除CO和CO2。氮气洗涤也是可能的。
因此，参考附图，根据本发明的用于通过烟气再循环优选共同生产氨和甲醇或者用于生产氨和甲醇二者之一的方法包括以下步骤：
-在一段重整器中处理烃类进料，
-在压缩机中压缩来自一段重整器的烟气的至少一部分，
-将该压缩的烟气与一段重整器流出物一起供应至二段重整器，
其中将富集的空气添加至一段重整器或二段重整器或其两者。
烃类进料是蒸汽和任选的预重整的烃类的混合物。这些烃类可来源于可用于重整器进料的任何烃源，例如天然气。
本发明的方法还可用于将更大量的CO2转化为尿素。更具体地，本发明的方法可用于制备生产尿素的轻质天然气。对于该目的而言，合成气中的CO2含量太低，目前通过生产大量的合成气来补偿该CO2缺乏，以获得必需的CO2量。过量的合成气用作燃料。
根据期望的最终产品，可将多个另外的方法步骤添加至上述步骤序列。如果例如期望合成氨和尿素，则包括以下另外的方法步骤：
-使二段重整器流出物通过变换工段，
-从变换流出物中除去CO2，
-进行CO2去除工段流出物的合成气净化，和
-在压缩机中将所得流压缩并将其转移到氨回路中以用于氨合成，
其中在CO2去除步骤中去除的CO2的量足以将氨合成中产生的所有氨转化为尿素。
为了共同生产氨、尿素以及任选的甲醇，还包括以下另外的方法步骤：
-任选地使二段重整器流出物或其部分通过变换工段，
-任选地从所述变换转化器流出物中去除所有CO2或其部分，
-在压缩机中压缩CO2去除工段流出物并任选地使其部分或全部通过甲醇合成工段，
-进行甲醇合成工段流出物的合成气净化，
-任选地在压缩机中进一步压缩所得流，和
-将所得流转移到氨回路以用于氨合成，
其中在CO2去除步骤中去除的CO2的量足以将氨合成中产生的所有氨或其部分转化为尿素。
如果期望仅生产甲醇，则包括以下另外的方法步骤：
-将二段重整器流出物直接供应至压缩机(C2)，和
-将来自压缩机C2的流出物通过甲醇合成工段，
其中合成气中的模数M(module)在2.0至3.0的范围内，优选在2.0至2.5范围内，且最优选在2.0至2.2的范围内。
可通过使用空气分离单元(ASU)来进行空气的富集。ASU将大气分离成它的主要组分，即氮气和氧气，并且有时也含氩气和其它稀有惰性气体。空气分离最常见的方法之一是低温蒸馏。建立低温ASU以提供氮气或氧气，并且通常共同生产氩气。在商业上使用诸如膜分离、变压吸附(PSA)和真空变压吸附(VPSA)的其它方法来从大气中分离单一组分。
通过以下实施例进一步说明本发明。
实施例
将根据本发明的烟气再循环方法与没有烟气再循环的两种现有技术方法进行比较，一种具有氨和甲醇的联合共同生产，一种仅具有氨的生产。
在下表1中，将根据本发明的方法与现有技术的氨和甲醇的联合生产以及现有技术的仅氨生产的两种方法进行比较。在表2中，将根据本发明的方法与现有技术的使用贫气的尿素生产进行比较。在后一种情况下，根据本发明的方法仅用于氨生产。
表1
表2
CO2排放只来自重整器排气管。对于现有技术的生产而言，即使假设其中的一部分可用于尿素生产，CO2排放量仍为约45MT/h，即是根据本发明的产量的两倍。
因此，从表1和表2的比较可以看出，通过使用本发明的方法，总的CO2排放量显著降低。
Claims (10)
1.一种用于共同生产氨、尿素以及任选的甲醇或用于生产氨或甲醇的方法，所述方法包括以下步骤：
-在一段重整器(PR)中处理烃类进料，
-在压缩机(C1)中压缩来自所述一段重整器的烟气的至少一部分，和
-将压缩的烟气与所述一段重整器流出物一起供应至二段重整器(SR)，
其中将富集的空气(EA)添加至所述一段重整器或所述二段重整器或其两者。
2.如权利要求1所述的方法，还包括以下步骤：
-使所述二段重整器流出物通过变换工段，
-从变换流出物中除去CO2，
-进行CO2去除工段流出物的合成气净化，以及
-在压缩机(C3)中将所得流压缩并将其转移到氨回路(AL)中以用于氨合成，
其中在所述CO2去除步骤中去除的CO2的量足以将所述氨合成中产生的所有氨转化为尿素。
3.如权利要求1所述的方法，还包括以下步骤：
-任选地使所述二段重整器流出物或其部分通过变换工段，
-任选地从变换转化器流出物中去除所有CO2或其部分，
-在压缩机C2中压缩CO2去除工段流出物并任选地使其部分或全部通过甲醇合成工段(M)，
-进行所述甲醇合成工段流出物的合成气净化，
-任选地在压缩机C3中进一步压缩所得流，
-将所得流转移到用于氨合成的氨回路(AL)，
其中在CO2去除步骤中去除的CO2的量足以将所述氨合成中产生的所有氨或其部分转化为尿素。
4.如权利要求1所述的方法，还包括以下步骤：
-将所述二段重整器流出物直接供应至压缩机(C2)，以及
-将来自所述压缩机C2的流出物通过甲醇合成工段，
其中所述合成气中的模数M为2.0至3.0；
其中所述模数M为化学计量数SN，SN＝([H2]-[CO2])/([CO2]+[CO])，并且其中所述气体的浓度为体积或摩尔分数。
5.如权利要求4所述的方法，其中所述模数M为2.0至2.5。
6.如权利要求4所述的方法，其中所述模数M为2.0至2.2。
7.如权利要求1所述的方法，其中通过使用空气分离单元(ASU)获得所述富集的空气。
8.如权利要求7所述的方法，其中所述ASU是基于膜分离技术。
9.如权利要求1-8中任一项所述的方法，其中所述烃类进料是蒸汽和任选的预重整烃类的混合物，所述烃类来源于可用于重整器进料的任何烃源。
10.如权利要求9所述的方法，其中所述烃类来源于天然气(NG)。
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| EP3224197A1 (en) | 2017-10-04 |
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