CN104640806B - 从硫化氢中回收氢的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 50
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004332 silver Substances 0.000 claims abstract description 33
- 229910052709 silver Inorganic materials 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 26
- 229910052946 acanthite Inorganic materials 0.000 claims description 19
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims description 17
- 229940056910 silver sulfide Drugs 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OCWNMDUAUUAHSJ-UHFFFAOYSA-N silver;sulfanylidenesilver Chemical compound [Ag].[Ag]=S OCWNMDUAUUAHSJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000002250 absorbent Substances 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000002745 absorbent Effects 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical class [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910000367 silver sulfate Inorganic materials 0.000 description 2
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- -1 H2S Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供使用负载银催化剂从硫化氢回收氢的方法，和使用该催化剂净化含硫化氢的气体流的方法。
Description
技术领域
本发明提供从硫化氢回收氢的方法，以及净化含硫化氢的气体流的方法。
背景技术
包括含硫物质(尤其是硫化氢(H2S))的气体流来自各种来源。烃类的天然来源可包括硫化氢，硫化氢是一种常见的添加剂，其为商业油气供应提供气味。此外，硫化氢经常存在于来自工业过程的废气流中。
含硫化合物，尤其是硫化氢，对许多化学过程有不利影响。由于H2S的存在，在加氢裂化、合成气处理、甲烷化、重整、蒸汽重整和加氢中使用的催化剂经常中毒。为了避免这些不利影响，要求能够有效地去除含硫化合物，特别是H2S，而对其它化学过程无显著影响的方法。最合适的是催化方法除硫。
此外，在烃类燃料气化以合成气体的期间，CO2和H2S的分离在酸性气体去除装置中进行。这应该发生，以便获得纯的CO2流，且H2S流不包含太多CO2。
WO2010/048201公开了一种从气体流中去除/回收硫的工艺。
US 4,582,819公开了一种新的催化吸收组合物，其可用于去除硫化氢。
Kiuchi H.等人.Int.J.Hydrogen Energy,Vol.7,No.6,pp.477-482,1982，公开了一种方法，其中H2S与金属或金属硫化物反应。在高温，即在600℃和大量的生成Ag2SO4的条件下，使所得的硫化物随后进行热分解或氧化。Schultz et al.Int.J.Hydrogen Energy,Vol.10,No.7/8,pp.439-446,1985，以更通用的方式并参考Kiuchi H.等人，公开了一种方法，其中H2S与金属或金属硫化物反应，所得的硫化物随后进行热分解或氧化。
在此领域的其它公开包括：US2010/0233054、WO 00/02645和JP2010051858A、JP2009185792A、US 5,451,268，以及S.Lilienfeld等人,Journal of the AmericanChemical Society,Vol.52,No.3,1March 1930,pp.885-892。
尽管在本领域中有新的进展，但仍然存在以下需要：从气体流中除去硫化氢的简单、有效的方法，该方法优选为催化工艺，并优选伴随生产工业上有用的副产品。
发明内容
由此，本发明提供两种方法。本发明的第一种方法是从硫化氢中回收氢的方法，包括以下步骤：
a.在至少200℃的温度下，使硫化氢与负载银反应，由此将银转化为硫化银，并释放氢；和
b.在低于450℃的温度下，使该硫化银进行轻度氧化，由此将硫化银转化为银和二氧化硫。
本发明的第二种方法是净化含硫化氢的气体流的方法。此方法包括以下步骤：
a.在至少200℃的温度下，使所述气体流通过负载银的床，从而使所述气体流中的硫化氢与所述银反应，由此将银转化成硫化银，并释放氢；和
b.在低于450℃的温度下，使硫化银进行轻度氧化，由此将硫化银转化成银和二氧化硫。
将银负载于负载材料上。负载银的银含量适当地为5-10wt％。负载材料适当地具有1-200m2/g的表面积和/或0.2-0.5cm3/g的孔隙度。负载材料具有直径为1-10mm的粒径。负载材料将在下文中更详细地描述。
本文中使用的术语"轻度氧化"指的是硫化银与氧化剂在低温，即低于450℃下反应。
轻度氧化适当地使用气态氧，优选大气稀释氧(atmospheric air dilute inoxygen)(1-5％)来进行。氧化步骤，步骤b，优选在200至400℃的温度下进行。
该方法可在烃类燃料气化成合成气体期间进行。适当地，步骤a和b在连续过程中一个紧接另一个的进行。
优选地，步骤a在250至500℃的温度下进行，更优选在300至450℃的温度下进行。
具体实施方式
本发明提供两种方法。第一种方法是从硫化氢中回收氢的方法。
第一种方法的第一步使硫化氢与负载银在至少200℃的温度，适当地在200℃至600℃的温度下反应。优选该步骤在250至500℃的温度，更优选在300至450℃的温度下进行。在此步骤中，将银(处于氧化状态0)转化为硫化银，并释放氢:
2Ag+H2S→Ag2S+H2
这一在约400℃下的过程的平衡常数约为30，且焓为0.079kcal/mol；本质上是热中性的。
在第一步中使用的银被负载于负载材料上。负载银由负载材料上的金属银颗粒构成。适当的负载材料包括氧化物如氧化铝、尖晶石如MgAl2O4、ZnO、TiO2。
负载银的银含量适当地为5-10wt％，5-15wt％或5-20wt％。这应该能够吸收0.5-2wt％的硫，以便温度升高能够保持可控。
该方法的第二步再生零氧化态下的银。在此第二步骤中，使硫化银在低于450℃下进行轻度氧化，由此将硫化银转化为银和二氧化硫。
Ag2S+O2→2Ag+SO2
如上文所述，术语"轻度氧化"涉及硫化银与氧化剂在低于450℃的温度下反应。为了避免过度产生Ag2SO4，轻度氧化适当地优选在200至400℃的温度下进行。
第二步中使用的氧化剂是最常用的气态氧，如大气稀释氧，例如0.5-5％vol。
本发明还提供净化含硫化氢的气体流的方法。该方法包括以下步骤：
步骤a：使所述气体流通过温度为至少200℃的银床，从而使气体流中的硫化氢与所述银反应，由此将银转化为硫化银并释放氢；和步骤b：使硫化银在低于450℃下进行轻度氧化，由此将硫化银转化为银和二氧化硫。
在烃类燃料气化成合成气体期间，本发明的此第二方法是最适合的，其中在酸性气体去除装置中进行CO2和H2S的分离。这应当发生，以便获得纯的CO2流，且H2S流不包含过多CO2。
上述对第一种方法的银、负载材料、氧化剂和有关的方法步骤描述的所有细节都同样适用于本发明的第二种方法。
对于本发明的两种方法，步骤a和b可在基本上连续的过程中一个紧接另一个地进行(即当认为银将要充分转化为硫化银时，硫化氢或者气体流可以被除去，取而代之的是氧化剂流)。
实施例1
适当的吸收剂可如下制备。用在lg水中含约2克硝酸银的浓缩液饱和适当的载体材料，该载体材料优选选自氧化物如氧化铝和尖晶石(MgAl2O4)或二氧化钛，且该载体材料优选具有1-200m2/g的表面积和0.2-0.5cm3/g的孔隙度。在450℃的温度下，将经饱和的载体干燥和煅烧，由此将硝酸银分解成银、氧化氮和氧。为了获得适当的银含量(通常为5-20％)，该浸渍可能重复。对于固定床应用，所述载体的粒径可在直径1至10mm之间变化。
实施例2
将含100kg银的lm3吸收剂在400℃下暴露于含0.1％的H2S的CO2的干流中。硫化氢的浓度降低至约40ppm。6小时内通过1000Nm3/h气体之后，吸收剂被部分饱和，且出口硫化氢浓度开始上升。
实施例3
将l00m3吸收剂在400℃下暴露于含2.5％的H2S的CO2的干流中。硫化氢的浓度降低至约0.1％，并产生约2.4％的H2。排出的气体被导引至酸性气体清除装置，并回收H2。24小时内通过1000Nm3/h气体之后，吸收剂被部分饱和。
实施例4
废吸收剂通过使用低氧含量的空气而再生，以保持温度低于450℃。入口温度可优选为200℃以上，且出口温度为375-425℃。排出的气体可被送至WSA(湿硫酸)单元，用于生产浓硫酸。
Claims (13)
1.从硫化氢中回收氢的方法，所述方法包括以下步骤：
a.在至少200℃的温度下，使硫化氢与负载银反应，由此将银转化为硫化银，并释放氢；和
b.在200℃至低于450℃的温度下，使所述硫化银进行轻度氧化，由此将硫化银转化为银和二氧化硫。
2.净化含硫化氢的气体流的方法，所述方法包括以下步骤：
a.在至少200℃的温度下，使所述气体流通过负载银的床，从而使所述气体流中的硫化氢与所述银反应，由此将银转化成硫化银，并释放氢；和
b.在200℃至低于450℃的温度下，使所述硫化银进行轻度氧化，由此将硫化银转化成银和二氧化硫。
3.根据权利要求1至2中任一项所述的方法，其中所述负载银的银含量为5-10wt％。
4.根据权利要求1至2中任一项所述的方法，其中负载材料具有1-200m2/g的表面积和/或0.2-0.5cm3/g的孔隙度。
5.根据权利要求1至2中任一项所述的方法，其中负载材料具有直径为1-10mm的粒径。
6.根据权利要求1至2中任一项所述的方法，其中所述轻度氧化使用气态氧进行。
7.根据权利要求6所述的方法，其中气态氧是大气稀释氧。
8.根据权利要求7所述的方法，其中在大气中稀释的氧为0.5-5体积％。
9.根据权利要求1至2中任一项所述的方法，其中步骤b在200至400℃的温度下进行。
10.根据权利要求1至2中任一项所述的方法，其中所述方法在烃类燃料气化至合成气体期间进行。
11.根据权利要求1至2中任一项所述的方法，其中步骤a和b在连续过程中一个紧接一个地进行。
12.根据权利要求1至2中任一项所述的方法，其中步骤a在250至500℃的温度下进行。
13.根据权利要求12所述的方法，其中步骤a在300至450℃的温度下进行。
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| RECOVERY OF HYDROGEN FROM HYDROGEN SULFIDE WITH METALS OR METAL SULFIDES;H. KIUCHI et al.;《Int. J. Hydrogen Energy》;19820101;第7卷(第6期);第477-482页 * |
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