CN103501877A - 原料气的净化方法 - Google Patents
原料气的净化方法 Download PDFInfo
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- CN103501877A CN103501877A CN201280015751.XA CN201280015751A CN103501877A CN 103501877 A CN103501877 A CN 103501877A CN 201280015751 A CN201280015751 A CN 201280015751A CN 103501877 A CN103501877 A CN 103501877A
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- 238000000034 method Methods 0.000 title claims abstract description 102
- 238000000746 purification Methods 0.000 title claims description 25
- 239000007789 gas Substances 0.000 claims abstract description 168
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 163
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 81
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 239000000446 fuel Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 238000002407 reforming Methods 0.000 claims description 9
- 239000003502 gasoline Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000005465 channeling Effects 0.000 claims description 3
- 150000004831 organic oxygen compounds Chemical class 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 238000002309 gasification Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005201 scrubbing Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 living beings Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Abstract
本发明公开了将含碳原材料转化为碳基液态或气态燃料的方法,包括步骤:a)将所述含碳原材料转化为碳基燃料;b)从步骤a)的过程的某个位置取出包含氢气、碳氧化物,例如一氧化碳或二氧化碳,和氮气的待净化的工艺气体;c)对所述待净化的工艺气体进行甲烷化反应,其中包含在所述待净化的工艺气体中的碳氧化物被转化为甲烷,提供甲烷化的工艺气体;d)将所述甲烷化的工艺气体导向氨合成以将所述气体中的氮气转化为氨,提供包含氨的工艺气体;e)从步骤d)的所述包含氨的工艺气体中取出液相氨,生成具有降低的氮气含量的净化的气体;f)将一些所述净化的气体导向步骤a)的过程的某个位置,其中碳基燃料中的碳的摩尔流量大于取出的氨的摩尔流量。
Description
本发明涉及原料气的净化。具体地,本发明涉及从原料气中去除氮气。
工业原料气,作为重整烃的原料或作为焦炉气,通常由含碳的原材料产生,例如煤的气化、石油焦、生物质和其类似物。
本文下面所使用的“原料气”应包含具有氢气、至少一种碳氧化物和氮气的任何气体。
通常,通过上述气化工艺或作为来自焦炭生产的废气(所谓的焦炉气)来获得这种原料气。
这些气体包含氢气,其特别是用作替代燃料或用于制备许多大宗化学品和许多液态或气态燃料的重要反应物。作为一个例子,在代用天然气(SNG)的制备中可使用气化原料气和焦炉气。
当使用SNG作为天然气的替代品时,如果要求SNG的高热值,则SNG必须具有高含量的甲烷并且在SNG的制备过程中产生的杂质的残留量必须很低。
通过费-托或有机氧化物-汽油(oxygenate to gasoline)工艺,也可以使原料气转化成液态燃料,例如汽油或柴油。在这个转化中,可能通过不期望的烃的重整,如一氧化碳到甲烷,可以使气流再循环以回收反应物。为了避免在循环流中不期望的组分积累,取出了吹扫气(purge gas)。一种这样的不期望的组分是惰性的氮气,由于它可能减少吹扫流,因此去除氮气是有利的,所述吹扫流从该过程除去原材料。
尽管通过用高纯氧操作气化炉,在来自气化的原料气中的氮气的浓度可被最小化,氮气仍然是煤、生物质、石油焦和在气化过程中使用的其他原料的组分并由此将被从原料中释放和转移到通过气化产生的原料气中。
类似的考虑也适用于焦化工艺。
二氧化碳和任选地硫化氢,如果存在于原料气中,可以用传统的酸性气体脱除工艺来去除,其中用二氧化碳和硫化氢的物理吸附剂处理所述气体,如已知的“低温甲醇洗(Rectisol)”或“塞勒克索尔(Selexol)”工艺,或用化学吸附剂处理所述气体,如已知的胺洗。用于减少原料气中的氮气含量的常见解决方法是深冷工艺,其中气体被冷却至氮的沸点以下。
建立和操作深冷是很昂贵的。因此,本发明提供了一种通过将氮气转化为氨来减少原料气中的不期望的杂质(包括氮气)的方法,与已知的方法相比氨更方便从原料气中去除,并且同时氨可以用作生产有价值的化学品,例如硫代硫酸铵或尿素,的原料。
为了允许氮气催化转化为氨,有必要在引入氨转化反应之前去除原料气中基本上全部的一氧化碳和二氧化碳(碳氧化物)和水。为了去除碳氧化物,在甲烷化步骤中处理原料气,其中在甲烷化催化剂存在下一氧化碳和二氧化碳与氢气反应生成甲烷。
然后,存在很少或不存在碳氧化物的所述甲烷化的气体进入公知的氨转化反应,且可将产生的氨作为液体与净化气流分离。液体形式的氨在本文中应理解为冷凝氨或溶解在水里的氨。
在其最广泛的实施方案中,本发明是一种用于将含碳原材料转化成液态或气态的碳基燃料的方法,
包括步骤:
a) 将所述含碳原材料转化为碳基燃料;
b) 从步骤a)的过程的某个位置取出包含氢气、碳氧化物,例如一氧化碳或二氧化碳,和氮气的待净化的工艺气体;
c) 对所述待净化的工艺气体进行甲烷化反应,其中包含在所述待净化的工艺气体中的碳氧化物被转化为甲烷,提供甲烷化的工艺气体;
d) 将所述甲烷化的工艺气体导向氨合成以将所述气体中的氮气转化为氨,提供包含氨的工艺气体;
e) 从步骤d)的所述包含氨的工艺气体中取出液相氨,产生具有降低的氮气含量的净化的气体;
f) 将一些所述净化的气体导向步骤a)的过程的某个位置,其中碳基燃料中的碳的摩尔流量大于取出的氨的摩尔流量。
在一个具体的实施方案中,碳基燃料中的碳的摩尔流量是取出的氨的摩尔流量的至少两倍,导致燃料产率增加的相关益处。
在一个用于生产费-托产品的具体实施方案中,所述待净化的工艺气体为费-托(FT)尾气,并且净化的气体被作为FT合成的原料或作为FT合成上游的部分氧化或重整步骤的原料再循环。所述费-托转化是本领域技术人员所公知的,且如通常已知的,可以在催化剂,如第VIII族金属,优选Fe, Co, Ru 和Ni, 或Mo,的存在下进行。
在一个用于合成甲醇或汽油的具体实施方案中,待净化的工艺气体取自用于合成甲醇或用于由有机氧化物合成汽油的合成回路,并且净化的气体被作为所述合成回路上游的部分氧化的原料或作为重整步骤的原料再循环。所述甲醇的合成是本领域技术人员所公知的,且如通常已知的,可以在催化剂(如,Cu)的存在下进行。
类似地,由有机氧化物(如,甲醇或二甲醚)合成汽油也是本领域技术人员所公知的,且如通常已知的,可以在催化剂,如沸石,优选ZSM5沸石,的存在下进行。
一个用于生产合成天然气的具体实施方案包括以下子步骤;
u) 从原料气中取出第一分流;
v) 使所述第一分流的一氧化碳通过水煤气变换工艺反应以形成氢气,提供变换气流;
w) 为了提供根据步骤b-f的所述待净化的工艺气体,在酸性气体脱除步骤中处理所述变换气流;
x) 为了获得原料流,在酸性气体脱除步骤中处理其余的原料气;
y) 引导所述净化的气体与至少一部分原料流合并;
z) 通过合成天然气的合成工艺将所述合并的流转化为代用天然气。
合成天然气的合成是本领域技术人员所公知的,且如通常已知的,可以在催化剂,如第VIII族金属,优选Ni或Ru,的存在下进行。
借助于已知的催化氨转化工艺,通过与进一步包含在所述原料气中的氢气的催化反应,氮气转化为氨。根据所述气体中的氮气的浓度,所述氨转化反应可以在单程通过操作(once-through operation)或以氨合成回路中进行。氨的合成是本领域技术人员所公知的,且如通常所知的,可以在催化剂,如Fe或Ru,的存在下进行。
当在氨合成回路中合成氨时,这个回路包括步骤
i) 为了使N2与H2反应以形成用于构成所述包含氨的气体的NH3,使一些氨合成回路气体与催化材料接触;
ii) 将包含氨的工艺气体分离成液相氨和净化的气体;
iii) 将额外量的(a further amount of)所述净化的气体导向步骤a)的过程,其中将甲烷化的待净化气体添加到所述氨合成回路的某个位置,例如紧接在催化材料的上游或下游。在取出氨的位置的上游添加包含水的所述甲烷化气体可能是有利的,因为即使少量的水的存在也能促进该去除。
在合成回路中合成氨具有增加氨的产率的益处,并且具有能够将甲烷化工艺气体与包含氨的工艺气体结合的益处,这样可以随所述氨去除甲烷化工艺气体中的水。
在一个实施方案中,通过传统的缩合或传统的氨水洗涤(aqueous ammonia wash)将产生的氨从原料气中去除,对于氨的收集来说,所述传统的缩合或传统的氨水洗涤具有是低本高效的工艺的益处。
随后可以通过,例如,冷却和冷凝水分离和/或通过与能够从气流中去除水分子的分子筛接触来干燥所述甲烷化的工艺气体。这种分子筛在本领域是已知的且通常用于干燥潮湿气体。
在一个实施方案中,原料气中的部分一氧化碳根据水煤气变换反应,通过与水反应转化形成氢气和二氧化碳,且由此该气体中的氢气的浓度增加而一氧化碳的含量减少,具有在甲烷化之前产生具有氢气和碳氧化物之间的更佳平衡的原料气的益处。如前所述,在随后的甲烷化步骤中一氧化碳含量将进一步减少。
当包括变换反应步骤时,需要酸性气体脱除步骤来去除二氧化碳,以避免产生的氢气在甲烷化过程中通过与二氧化碳反应而消耗。当没有变换反应步骤,在酸性气体脱除步骤中对所述气体的处理时,即二氧化碳和硫化氢的量(如果进一步存在于原料气中)通过化学或物理吸附或根据如上所述的已知方法的吸附来降低。这具有提供使用催化剂的可能性的效果,所述催化剂更有效但会由于一氧化碳和硫的存在而中毒。
在更具体的实施方案中,为了将碳氧化物转化为甲烷,可包括在酸性气体脱除之前的甲烷化步骤,所述甲烷不会在酸性气体脱除步骤中被取出。这具有在净化的气体中提供更高水平的碳的相关益处。
SNG是通过碳氧化物与氢气的催化甲烷化产生的。如上所述,在待净化的工艺气体的净化过程中碳氧化物被转化为甲烷。如果容许最终SNG产品中含有一定量的氮气,根据本发明的另一实施方案,可以通过在原料气净化之前从原料气中取出一个分流和在酸性气体脱除步骤中单独处理该分流以从该分流中减少或去除二氧化碳含量来增加甲烷的产量。对于SNG生产,原料中的 (H2- CO2) / (CO+CO2)之比任选地为约3,其中H2、CO和CO2 代表该给定组分的摩尔流量。
在酸性气体脱除中,也可能存在于原料气中的硫化氢在化学或物理洗涤中也会被吸附。用过的洗涤液可通过解吸二氧化碳和硫化氢来再生。
一部分解吸的二氧化碳可被再循环至净化的原料气以用于碳基燃料的合成,具有增加所述燃料产率的益处。
一部分解吸的二氧化碳也可用于由氨合成尿素,具有尿素是比氨更有价值的产品的益处。
解吸的硫化氢通过与在原料气的净化中获得的氨反应可用于硫代硫酸铵的制备,如,例如,在欧洲专利no.1 375 422中所描述的。
本发明的方法还可用于减少循环物料中的氮气的浓度,由此提供所述循环的减少和,可能地,待吹扫体积的减少,特别对于其中在甲烷化步骤形成额外量的甲烷是有利的或其可在下游,例如,在重整过程(如自热重整或水蒸汽重整)中被转化的工艺来说。
图l显示了一个实施方案,其中利用本发明的净化方法将含碳的原材料转化为液态燃料。
图2显示了一个实施方案,其中利用本发明的净化方法将含碳原材料转化为合成天然气。
图 1显示了本发明的一个具体实施方案,其中将含碳原材料作为原料气100提供给用于合成液体燃料104的工艺。所述包含氮气100的原料气在反应器102中通过催化反应转化成燃料104,如甲醇、汽油、柴油和石脑油。在燃料生产过程中氢气和一氧化碳被消耗,产生富含氮气的待净化的工艺气体流。
如果要求将CO转化为氢气以确保在甲烷化步骤116中按照以下反应将CO和CO2转化为甲烷之后氢气过量,可把所述待净化的工艺气体106导向水煤气变换阶段108:
CO + 3H2 = H2O + CH4,
CO2 + 4H2 = 2H2O + CH4。
氢气的合理过量还将确保在下游的氨合成118中氮气部分转化成氨。进入下游的甲烷化反应器116的分子氢的最佳摩尔流量可以如下计算:
H2 > 3*CO + 4*CO2 + 3*N2, 其中H2、CO、CO2、N2代表给定组分的摩尔流量。然而,通过形成NH3部分地去除N2,该方法在低至H2 = 3*CO + 4*CO2水平的更少的氢气下也可以工作,其中所有氢气将被用于甲烷化,且不会发生N2的去除。
可以通过传统的方法从所述变换气中去除水,包括在冷凝器110中冷却变换气至约40℃,然后分离冷凝水。
通过在酸性气体洗涤112中去除过量的CO2 114,根据上面的反应式调节CO2含量以确保过量的氢气进入甲烷化反应器。
将该部分净化的工艺气体送至甲烷化步骤116以将CO和CO2转化为甲烷,因为这两种组分对于氨催化剂是有毒的。
包含氢气、氮气和甲烷的甲烷化的工艺气体被送往氨合成回路118以将氮气至少部分转化为氨,所述氨可以在操作在约-5℃下的冷凝器中从包含氨的气体流中分离,形成具有降低浓度的氮气的净化的气体流和氨的液体流119。额外的氨水洗涤120可被用来去除剩余的氨122。
然后,在124中重整所述净化的气体流以将甲烷转化为合成气,即CO和H2,产生用于102中的燃料合成的重整的净化的气体。通过吹扫流避免了其他杂质,如Ar,在合成气中的积累。
如果在重整的净化的气体中CO2的浓度过高,那么可以借助酸性气体脱除装置126将其除去。
图2显示了本发明的另一实施方案,其中将含碳原材料作为含有氮气的原料气200提供给用于生产合成天然气204的工艺。
当在随后的阶段按照以下反应将CO和CO2转化为甲烷时,为了将CO和水转化为氢气和CO2以确保氢气的过量,将第一部分粗合成气体送往水煤气变换阶段202:
CO + 3H2 = H2O + CH4
CO2 + 4H2 = 2H2O + CH4
氢气的合理过量还将确保在下游的氨合成中氮气部分转化成氨。进入下游的甲烷化反应器216中的分子氢的最小摩尔流量可以如下计算:
H2 > 3*CO + 4*CO2 + 3*N2,其中H2, CO, CO2, N2代表给定组分的摩尔流量,但是如上所述,只要H2 > 3*CO + 4*CO2,所述过程将去除一些N2。
在冷凝器210中通过将变换气冷却至约40℃并随后分离冷凝水来从所述变换气中去除水。
通过在酸性气体洗涤212中去除过量的CO2 214,根据上面的反应式调节CO2含量以确保过量的氢气进入甲烷化反应器中。
将该部分净化的待净化工艺气体送至甲烷化步骤216以将CO和CO2转化为甲烷,因为这两种组分对于氨催化剂是有毒的。
包含氢气、氮气和甲烷的甲烷化的工艺气体被送至氨合成回路218以将氮气部分地转化为氨,所述氨可以在氨水洗涤220中从气体流中分离,形成具有降低浓度的氮气的净化的气体流和氨流222。
未导向水煤气变换的那部分合成气在酸性气体脱除阶段226中处理以去除酸性气,如H2S和CO2,形成处理的合成气。
然后将该处理的合成气流与净化的气体流合并以形成用于SNG合成装置230的原料气,其中 (H2-CO2) / (CO2+CO) ~3。
实施例
在涉及费-托方法的本发明的第一个实施例中,根据图1所示的本发明的实施方案净化了N2含量为24%的待净化的工艺气体。在所述方法中气体组成将如表1所示。
在第二个实施例中,待净化的气体的组成相似,但是对净化的气体中的CO含量的要求更高。因此在变换反应器上游包括了进一步的甲烷化反应器。所得气体组成如表2显示。
最后,在表3中提供了在待净化的工艺气体中具有较低氮气浓度的第三个实施例。
Claims (13)
1.将含碳原材料转化为液态或气态的碳基燃料的方法,包括步骤:
a) 将所述含碳原材料转化为碳基燃料;
b) 从所述步骤a的过程中的位置取出包含氢气、碳氧化物,如,一氧化碳或二氧化碳,和氮气的待净化的工艺气体;
c) 对所述待净化的工艺气体进行甲烷化反应,其中包含在所述待净化的工艺气体中的碳氧化物被转化为甲烷;提供甲烷化的工艺气体;
d) 将所述甲烷化的工艺气体导向单程通过氨合成或氨合成回路以将所述气体中的氮气转化为氨,提供包含氨的工艺气体;
e) 从步骤d)的所述包含氨的待净化工艺气体中取出液相氨,产生具有减少的氮气含量的净化的气体;和
f) 将一些所述净化的气体导向步骤a的过程中的位置,
其中碳基燃料中的碳的摩尔流量大于取出的氨的摩尔流量。
2.根据权利要求1所述的方法,其中所述碳基燃料中的碳的摩尔流量是取出的氨的摩尔流量的至少两倍。
3.根据权利要求1或2所述的方法,其中所述待净化的工艺气体为费-托 (FT)尾气且所述净化的气体被作为FT合成的原料或作为FT合成上游的部分氧化或重整步骤的原料再循环。
4.根据权利要求1或2所述的方法,其中所述待净化的工艺气体取自用于合成甲醇或用于由有机氧化物合成汽油的合成回路,并且所述净化的气体被作为所述合成回路上游的部分氧化或重整步骤的原料再循环。
5.根据权利要求1或2的方法,其中步骤a包括以下子步骤;
u) 从所述原料气中取出第一分流;
v) 使所述第一分流的一氧化碳通过水煤气变换工艺反应以形成氢气,提供变换气流;
w) 为了提供形成步骤b-f中的所述待净化的工艺气体,在酸性气体脱除步骤中处理所述变换气流;
x) 为了获得原料流,在酸性气体脱除步骤中处理其余的原料气;
y) 引导一些所述净化的气体与至少一部分所述原料流合并;
z) 通过SNG工艺将所述合并的流转化为代用天然气。
6.根据权利要求1、2、3、4或5所述的方法,其中所述氨合成回路包括步骤:
i) 为了使N2与H2反应以形成用于构成所述包含氨的气体的NH3,使一些氨合成回路气体与催化材料接触;
ii) 将包含氨的待净化工艺气体分离成液相氨和净化的气体
iii) 将额外量的所述净化气体导向所述步骤a)的过程;
其中将甲烷化的待净化工艺气体添加到所述氨合成回路中的位置。
7.根据权利要求1、2、3、4、5或6所述的方法,包括通过在步骤c)之前对所述原料气进行水煤气变换反应,去除包含在所述原料气中的一部分二氧化碳的进一步的步骤。
8.根据权利要求1、2、3、4、5、6或7所述的方法,包括在步骤c)中的所述甲烷化之前对所述待净化的工艺气体进行用于减少水含量的步骤的进一步的步骤。
9.根据权利要求1、2、3、4、5、6、7或8所述的方法,进一步地包括在步骤c)中的所述甲烷化之前的酸性气体脱除步骤。
10.根据权利要求1、2、3、4、5、6、7、8或9所述的方法,进一步包括在步骤e)下游的重整甲烷以形成二氧化碳和氢气的步骤。
11.根据权利要求1、2、3、4、5、6、7、8、9或10所述的方法,其中从步骤e)中的所述气体中除去的所述氨被用于生产硫代硫酸铵。
12.根据权利要求1、2、3、4、5、6、7、8、9、10或11所述的方法,其中从步骤e)中的所述气体中除去的所述氨被用于生产尿素。
13.根据权利要求4、6或7所述的方法,其中在酸性气体洗涤中去除的所述二氧化碳的至少一部分被从酸性气体洗涤步骤回收并与用于生产尿素的液氨合并。
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PCT/EP2011/001572 WO2012130258A1 (en) | 2011-03-29 | 2011-03-29 | Method for the purification of raw gas |
PCT/EP2012/001376 WO2012130450A1 (en) | 2011-03-29 | 2012-03-29 | Method for the purification of raw gas |
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CN109153565A (zh) * | 2016-05-03 | 2019-01-04 | 卡萨尔公司 | 生产合成气的方法 |
CN110799451A (zh) * | 2017-08-24 | 2020-02-14 | 托普索公司 | 自热氨裂化方法 |
CN113249147A (zh) * | 2021-06-30 | 2021-08-13 | 杨皓 | 一种焦炉煤气联产lng与合成氨的改进工艺 |
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CN104232193A (zh) * | 2013-06-07 | 2014-12-24 | 中国海洋石油总公司 | 一种由炭质材料生产甲烷联产液体燃料的方法 |
US10618818B1 (en) * | 2019-03-22 | 2020-04-14 | Sure Champion Investment Limited | Catalytic gasification to produce ammonia and urea |
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