CN109382105B - 硫化氢选择氧化催化剂及其制备方法 - Google Patents
硫化氢选择氧化催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 6
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- 238000000034 method Methods 0.000 claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 239000002994 raw material Substances 0.000 claims abstract description 21
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000292 calcium oxide Substances 0.000 claims abstract description 20
- 239000000378 calcium silicate Substances 0.000 claims abstract description 19
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 19
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- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical group [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 23
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
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- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 claims description 2
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- 239000000377 silicon dioxide Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen sulfide Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于硫磺回收技术领域,具体涉及一种硫化氢选择氧化催化剂及其制备方法。载体原料包括偏钛酸、二氧化硅粉和硅酸钙,以氧化铁和氧化钙为活性组分;二氧化硅粉为比表面积为40‑60m2/g的气相法二氧化硅粉。采用本发明载体保证催化剂具有合适的孔结构,避免在选择氧化段催化剂发生克劳斯逆反应,降低了催化剂对水蒸气、氧含量的敏感性;本发明催化剂具有高活性、受过程气中水蒸气、氧气含影响量不敏感、侧压强度高,H2S转化率高的特点。使用本催化剂硫化氢转化率可达到95%以上,硫磺收率可达90%以上,侧压强度达到120N/cm以上,从而提高硫回收装置的硫回收率,具有显著的经济效益和社会效益。
Description
技术领域
本发明属于硫磺回收技术领域,具体涉及一种硫化氢选择氧化催化剂及其制备方法。
背景技术
在硫回收工艺中,直接氧化类工艺以操作简单、硫回收率高而受到广泛关注。它采用特殊的催化剂,将过程气中的硫化氢直接催化氧化为元素硫。这种工艺既可处理贫酸性气,又可处理常规Claus尾气。直接氧化法工艺较多,如德国Linder公司的Clinsulf~Do工艺、Parsons公司的Hi~Activity工艺、BASF公司的Catasulf工艺等。其中应用最广泛的为Super Claus工艺,该工艺是目前最成功、应用最广的直接氧化类工艺。
Super Claus工艺是直接氧化工艺中的一种,是目前最成功、应用最广的直接氧化类工艺。Super Claus工艺采用通过改变以往单纯提高H2S与SO2反应进程的方法,在传统克劳斯转化之后,最后一级转化段使用新型硫化氢选择性氧化催化剂,实际上是一种尾气处理工艺,以此来改进克劳斯工艺的硫回收技术。SuperClaus工艺主反应为硫化氢与氧气反应生成硫和水,且该反应不受热力学平衡限制,在传统克劳斯转化之后,最后一级转化段使用硫化氢选择性氧化催化剂,提高装置的硫回收率。目前,国内外SuperClaus工艺己建装置有100多套,发展迅速。
目前,国内外开发的硫化氢选择性氧化催化剂的牌号较少,总体来说,现有催化剂对硫磺的收率不高,存在以下问题:(1)催化剂对过程气中氧含量敏感,氧含量高造成催化剂选择性变差,氧含量低影响催化剂转化率;(2)催化剂对硫磺的选择性差,造成对硫的收率较低,影响硫磺装置的硫回收率;(3)催化剂对水敏感,催化活性受水蒸气含量影响较大,有的催化剂要求在低水含量(体积含量小于5%)或无水的条件下使用,但经二级克劳斯反应后气体中水蒸气含量在25%以上,无法满足此类催化剂要求;(4)催化剂强度差,侧压强度一般低于100N/cm,不利于装置长周期运行。
US4818740公开一种选择氧化含硫化合物特别是硫化氢成为元素硫的催化剂,该催化剂以α氧化铝为载体,铁和铬的氧化物为活性组分,此专利制备的催化剂具有较高的转化率和选择性。但工业应用实际结果表明,催化剂实际转化率为95%左右,选择性不到80%。由于选择性较差,只能处理含硫化氢含量较低的气体。
CN200810157750.4公开一种选择性氧化硫化氢成为元素硫的催化剂及工艺。该催化剂包括载体和活性组分,活性组分采用三氧化二铁和/或三氧化二铬,载体为二氧化钛和三氧化二铝的混合氧化物,载体中二氧化钛含量为60~95%。该催化剂用于含硫化氢混合气体的选择氧化硫化氢为元素硫的反应。反应条件为:反应温度160~280℃,反应压力0.02~10.0MPa,气体空速为400~2000h~1,H2S≤3.0%(Vol%),O2/H2S(摩尔比)=0.6~3.0。由于该催化剂使用二氧化钛载体,对水敏感,只能用于处理无水或低水含量(小于5%)的气体。
发明内容
针对现有技术的不足,本发明的目的是提供一种硫化氢选择氧化制硫催化剂,具有高活性,受过程气中水蒸气、氧气含影响量不敏感,侧压强度高,H2S转化率高,硫磺收率高,选择性高的优点;本发明还提供其制备方法。
本发明所述的硫化氢选择氧化催化剂,载体原料包括偏钛酸、二氧化硅粉和硅酸钙,以氧化铁和氧化钙为活性组分;二氧化硅粉为比表面积为40-60m2/g的气相法二氧化硅粉。
本发明载体原料包括偏钛酸和比表面积为40-60m2/g的气相法二氧化硅粉,保证催化剂具有合适的孔结构,避免在选择氧化段催化剂发生克劳斯逆反应,降低了催化剂对水蒸气、氧含量的敏感性。
本发明通过活性组分氧化铁、氧化钙含量的优化调变来提高催化剂对硫磺的收率,硅酸钙作为助剂的加入来提高催化剂强度。
以催化剂重量100%计,催化剂包括以下重量分数的成分:
Fe2O3含量优选为4~6%。
偏钛酸优选为锐钛矿型偏钛酸。
载体孔容大于0.6ml/g,平均孔径大于25nm,用压汞法(GB/T21650.1~2008)测定孔容及平均孔径。选择该孔容、孔径,有利于硫分子快速通过,降低生成SO2的风险,提高硫磺产率。
本发明以二氧化硅和氧化钛为载体主要原料,挤出成型过程加入活性组分氧化钙和助剂硅酸钙,经挤条、烘干、焙烧制备成载体;然后以氧化铁为活性组分,采用浸渍法制备而成。
本发明所述的硫化氢选择氧化催化剂的制备方法,包括以下步骤:
(1)将二氧化硅粉、偏钛酸、氧化钙、硅酸钙与扩孔剂混合均匀,再加入粘结剂和水,一起混捏后,经挤条、干燥、焙烧制成载体;
(2)将可溶性铁盐浸渍载体后,干燥、焙烧制成催化剂。
其中:
扩孔剂为田菁粉、聚乙烯醇、聚丙烯酰胺、石墨或淀粉,优选田菁粉,扩孔剂加入量为催化剂重量含量的2~5%,优选为3%。
粘结剂为硝酸、柠檬酸或草酸,优选硝酸。
步骤(1)焙烧温度为500~900℃,优选700℃。
可溶性铁盐为柠檬酸铁铵、EDTA铁铵或硝酸铁,优选柠檬酸铁铵。
步骤(2)焙烧温度为300~600℃,优选温度为400℃。
可溶性铁盐浸渍载体为等体积浸渍。
作为一种优选的技术方案,本发明所述的硫化氢选择氧化催化剂的制备方法,包括以下步骤:
(1)将二氧化硅粉、偏钛酸粉、氧化钙、硅酸钙与扩孔剂混合均匀,再加入粘结剂和水,加一起混捏后,用条型孔板挤条成型,于110~150℃烘干2~4小时,于700℃焙烧2~5小时,制成载体;
(2)可溶性铁盐加入去离子水制成活性组分浸渍液,取活性组分浸渍液浸渍载体10分钟~3小时,最好是0.5~1小时,于110~150℃烘干2~6小时,于300~600℃焙烧2~6小时,即得催化剂。
本发明制得的催化剂孔容大于0.5ml/g,比表面大于20m2/g。
条型孔板为ф3mm条型孔板。
综上所述,本发明具有以下优点:
(1)本发明载体原料包括偏钛酸和比表面积为40-60m2/g的气相法二氧化硅粉,保证催化剂具有合适的孔结构,避免在选择氧化段催化剂发生克劳斯逆反应,降低了催化剂对水蒸气、氧含量的敏感性。本发明通过活性组分氧化铁、氧化钙含量的优化调变来提高催化剂对硫磺的收率,硅酸钙作为助剂的加入来提高催化剂强度。
(2)采用本发明制备的催化剂具有高活性、受过程气中水蒸气、氧气含影响量不敏感、侧压强度高,H2S转化率高的特点。使用本催化剂硫化氢转化率可达到95%以上,硫磺收率可达90%以上,侧压强度达到120N/cm以上,从而提高硫回收装置的硫回收率,具有显著的经济效益和社会效益。
(3)本催化剂可用于处理石油炼制、天然气净化及煤化工等行业产生的硫化氢气体,提高硫磺装置的硫回收率。
附图说明
图1是本发明实施例制备的催化剂的活性评价装置流程图。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例1
称取650.6克比表面为50m2/g气相法二氧化硅粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1300克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为38m2/g,孔容为0.66ml/g,平均孔径为41nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为32m2/g,孔容为0.62ml/g,平均孔径为36nm。
实施例2
称取500.6克比表面为40m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、500克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1100克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为43m2/g,孔容为0.64ml/g,平均孔径为39nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到600克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为36m2/g,孔容为0.60ml/g,平均孔径为33nm。
实施例3
称取750.7克比表面为60m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、187.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1420克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为31m2/g,孔容为0.69ml/g,平均孔径为43nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到600克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为25m2/g,孔容为0.65ml/g,平均孔径为38nm。
实施例4
称取620.6克比表面为45m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1250克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为37m2/g,孔容为0.66ml/g,平均孔径为41nm。
将488克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为30m2/g,孔容为0.61ml/g,平均孔径为35nm。
实施例5
称取680.6克比表面为55m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1350克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为38m2/g,孔容为0.66ml/g,平均孔径为41nm。
将122克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为33m2/g,孔容为0.63ml/g,平均孔径为37nm。
实施例6
称取640.6克比表面为50m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、40克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1300克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为37m2/g,孔容为0.66ml/g,平均孔径为41nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为31m2/g,孔容为0.62ml/g,平均孔径为36nm。
实施例7
称取660.6克比表面为50m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、20克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1300克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为39m2/g,孔容为0.66ml/g,平均孔径为41nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为33m2/g,孔容为0.62ml/g,平均孔径为36nm。
对比例1
称取680.6克比表面为50m2/g气相法二氧化硅粉粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1340克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为39m2/g,孔容为0.67ml/g,平均孔径为41nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为33m2/g,孔容为0.63ml/g,平均孔径为36nm。
对比例2
称取650.6克比表面为180m2/g气相法二氧化硅粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1600克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为136m2/g,孔容为0.72ml/g,平均孔径为21nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为124m2/g,孔容为0.69ml/g,平均孔径为19nm。
对比例3
称取650.6克比表面为90m2/g气相法二氧化硅粉(氧化硅含量为99.9%)、312.5克纯度为98%的锐钛矿型偏钛酸、20.2克纯度为99%的氧化钙、30克硅酸钙、30克田菁粉,混合均匀形成物料A。50克浓硝酸与1600克蒸馏水混合均匀,加入到物料A中,在挤条机上挤条成型,在120℃干燥4小时,在700℃焙烧4小时,由此制得的载体为条形,载体比表面积为76m2/g,孔容为0.69ml/g,平均孔径为23nm。
将305克柠檬酸铁铵(FeC6H5O7.NH4OH)加入到1200克水中,混合均匀,用得到的溶液浸渍制得的载体,浸渍时间为1个小时,在120℃干燥4小时,在500℃下焙烧4小时,由此制得的催化剂比表面积为67m2/g,孔容为0.65ml/g,平均孔径为22nm。
对实施例1-7和对比例1-3制备的催化剂按下列方法进行活性评价:
微反装置的反应器由内径为20mm的不锈钢管制成,反应器放置在恒温箱内。催化剂装填量为10ml,上部装填相同粒度的石英砂进行混合预热。采用日本岛津GC—2014气相色谱仪在线分析反应器入口及出口气体中H2S、SO2和O2的含量,采用GDX—301担体分析硫化物,采用5A分子筛分析O2含量,柱温120℃,采用热导检测器,以氢气作载气,柱后流速25ml/min。
催化剂活性评价装置流程图如图1所示。
以2H2S+O2→2S+2H2O、2H2S+3O2→2SO2+2H2O为指标反应,考察催化剂的催化活性,入口气体组成为H2S 1%、O2 1.5%、H2O 30%,其余为N2,气体体积空速为1600h-1,反应温度为200℃,根据下式计算催化剂的H2S转化率ηAct:
其中M0,M1则分别代表入口及出口处H2S的体积浓度。
根据下式计算催化剂的H2S转化生成硫磺的选择性ηSel:
其中M0,M1则分别代表入口及出口处H2S的体积浓度,C0为出口处二氧化硫的体积浓度。
根据下式计算催化剂的H2S转化生成硫磺的产率ηYld:
ηYld=ηAct×ηSel
对实施例1-7和对比例1-3制备的催化剂的活性评价结果见表1。
表1
对实施例1、对比例2制备的催化剂按下列方法进行活性评价,具体数据见表2。
入口气体组成为H2S 1%、H2O 30%,其余为N2,O2分别为1.5%、2%、3%,气体体积空速为1600h-1,反应温度为200℃,考察H2S转化率ηAct、选择性ηSel、硫磺的产率ηY。
表2
对实施例1、对比例2制备的催化剂按下列方法进行活性评价,具体数据见表3。
入口气体组成为H2S 1%、O2 1.5%,H2O分别为30%、35%、40%,其余为N2,气体体积空速为1600h-1,反应温度为200℃,考察H2S转化率ηAct、选择性ηSel、硫磺的产率ηY。
表3
Claims (9)
2.根据权利要求1所述的硫化氢选择氧化催化剂,其特征在于:载体孔容大于0.6ml/g,平均孔径大于25nm。
3.根据权利要求1所述的硫化氢选择氧化催化剂,其特征在于:偏钛酸为锐钛矿型偏钛酸。
4.一种权利要求1-3任一所述的硫化氢选择氧化催化剂的制备方法,其特征在于:包括以下步骤:
(1)将二氧化硅粉、偏钛酸、氧化钙、硅酸钙与扩孔剂混合均匀,再加入粘结剂和水,一起混捏后,经挤条、干燥、焙烧制成载体;
(2)将可溶性铁盐浸渍载体后,干燥、焙烧制成催化剂。
5.根据权利要求4所述的硫化氢选择氧化催化剂的制备方法,其特征在于:扩孔剂为田菁粉、聚乙烯醇、聚丙烯酰胺、石墨或淀粉,扩孔剂加入量为催化剂重量含量的2~5%。
6.根据权利要求4所述的硫化氢选择氧化催化剂的制备方法,其特征在于:粘结剂为硝酸、柠檬酸或草酸。
7.根据权利要求4所述的硫化氢选择氧化催化剂的制备方法,其特征在于:步骤(1)焙烧温度为500~900℃;步骤(2)焙烧温度为300~600℃。
8.根据权利要求4所述的硫化氢选择氧化催化剂的制备方法,其特征在于:可溶性铁盐为柠檬酸铁铵、EDTA铁铵或硝酸铁。
9.根据权利要求5-8任一所述的硫化氢选择氧化催化剂的制备方法,其特征在于:包括以下步骤:
(1)将二氧化硅粉、偏钛酸粉、氧化钙、硅酸钙与扩孔剂混合均匀,再加入粘结剂和水,加一起混捏后,用条型孔板挤条成型,于110~150℃烘干24小时,于700℃焙烧2~5小时,制成载体;
(2)可溶性铁盐加入去离子水制成活性组分浸渍液,取活性组分浸渍液浸渍载体10分钟~3小时,于110~150℃烘干2~6小时,于300~600℃焙烧2~6小时,即得催化剂。
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