CN109647380A - 一种用于富co气脱氧的复合氧化物催化剂及其制备方法和应用 - Google Patents
一种用于富co气脱氧的复合氧化物催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 16
- 239000001301 oxygen Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical group [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 230000003020 moisturizing effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 231100000572 poisoning Toxicity 0.000 abstract description 11
- 230000000607 poisoning effect Effects 0.000 abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- -1 converter gas Chemical compound 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101000640743 Ralstonia solanacearum (strain GMI1000) Tryptophan 2,3-dioxygenase 2 Proteins 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
本发明公开了一种用于富CO气脱氧的复合氧化物催化剂及其制备方法和应用,该复合氧化物脱氧催化剂结构为aAxOy·bGxOy·mDxOy·nZrO2,其中A为过渡金属镍、锰中的一种,G为锌、铁、钙和镁中的一种,D为稀土金属铈、镧中的一种。以催化剂的总质量计,AO为30%~52%,GxOy为25%~47%,DxOy为3%~8%,ZrO2为20~35%。该复合氧化物脱氧催化剂可用于转炉气等富CO气脱氧,具有低温脱氧活性好、脱氧精度高、抗硫化物中毒能力强的优点,适于工业应用。
Description
技术领域
本发明涉及一种复合氧化物脱氧催化剂及其制备方法,特别适用于转炉气等富CO气脱氧所需复合氧化物脱氧催化剂及其制备方法和应用。
背景技术
转炉气生产甲醇和乙二醇项目,因其循环利用资源,经济效益和社会效益显著从而成为近年来煤化工的一个热点,倍受青睐。由于其中氧含量经常在0.5~1.0%波动,有时高达1.5%,在脱硫过程中容易造成床层飞温、加氢脱硫催化剂的反硫化以及后续合成催化剂的氧中毒失活,因此转炉气脱氧是其资源化应用的前提。
采用脱氧催化剂,可使转炉气等富CO气中的氧气与CO反应转化为CO2而除去。发生反应的化学方程式如下:
可能出现的副反应有:
2 CO = C↓+ CO2 (2)
CO + 3H2 = CH4 + H2O (3)
通常的Pd/Al2O3、Pt/Al2O3等贵金属脱氧催化剂在富CO气氛的脱氧反应温度一般在170℃左右,深度脱氧温度高至200℃以上;MoS-CoS- Al2O3类的硫化型脱氧剂,其使用温度一般在220℃以上。这两类脱氧催化剂使用时,若入口氧高达1.0%,脱氧反应(1)放热会使床层温度高于300℃,出现放热的副反应(2)、(3)就会导致飞温,使催化剂烧结失活;反应(2)所产生的碳也会堵塞催化剂孔道,引起催化剂失活。因此,Pd/Al2O3、Pt/Al2O3和MoS-CoS- Al2O3等催化剂不适于转炉气等富CO气脱氧。
专利CN1220302A提供一种高浓度CO合成气脱氧催化剂,能够在较低的温度下催化脱除O2,但其为负载型,活性组分负载量有限,并且不耐硫,容易硫中毒失活,因此很难维持脱氧活性的稳定性。
综上所述,现有的技术不能提供兼备低温脱氧活性好、抗硫化物中毒能力强、脱氧活性稳定等三大优点的脱氧催化剂,难以满足转炉气等富CO气脱氧需要。
发明内容
本发明的目的是提供一种新的复合氧化物脱氧催化剂。该催化剂具有低温脱氧活性好、抗硫化物中毒能力强、脱氧活性稳定等优点。本发明的另一个目的是提供一种上述复合氧化物脱氧催化剂的制备方法和应用。
本发明解决其技术问题所采用的技术方案为:一种复合氧化物脱氧催化剂aAxOy·bGxOy·mDxOy·nZrO2,其中A为过渡金属镍、锰中的一种,G为锌、铁、钙和镁中的一种,D为稀土金属铈、镧中的一种。过渡金属镍、锰与氧化锆协同作用,使复合氧化物具备良好的低温脱氧催化活性;G为锌、铁、钙和镁中的一种,易于与硫化物反应,增强脱氧催化剂的抗硫性能;稀土金属铈、镧可调节复合氧化物的酸碱性,有效抑制CO歧化副反应,提高复合氧化物脱氧稳定性。aAxOy·bGxOy·mDxOy·nZrO2低温脱氧活性好,抗硫化物中毒能力强、脱氧活性稳定。
本发明复合氧化物脱氧催化剂的制备方法,可通过包括下述主要步骤方法制备:
(1)共沉淀制得脱氧催化剂前驱体。(a)称取一定量的镍或锰的硝酸盐或硫酸盐以及硝酸锆共两种盐溶于水中,形成溶液。(b)将计算量的沉淀剂配成溶液,加入步骤(a)配制的溶液,搅拌反应。然后,老化3~8h。(c)将步骤(b)混合物过滤,洗涤后,在90~130℃烘干1~3h;得到复合氧化物前驱体;
(2)采用混捏法制得复合氧化物成品。(a)将计算量的稀土金属铈、镧中的一种的硝酸盐和一定量的水配成溶液。(b)将步骤(1)得到的复合氧化物前驱体加入一定量的锌、铁、钙和镁中的一种,研磨均匀再添加(a)溶液,搅拌碾压均匀后挤压成型,保湿放置8~12h后,经80~120℃干燥2~5h,再在450~650℃焙烧3~5h后制得复合氧化物脱氧催化剂。
与现有技术比较,本发明的有益效果是:(1)具备良好的低温脱氧催化活性。脱氧的重要步骤是催化剂的某一组分对氧有中等强度的化学吸附,金属元素中有d5、d7、d8、d10结构的过渡金属无疑是合适的。采用d5和d8结构的活性组分镍或锰,并与易于产生氧空穴的二氧化锆载体相互作用,大大降低了脱氧的活性温度。(2)抗硫化物中毒能力强。aAxOy·bGxOy·mDxOy·nZrO2的复合氧化物中,G为锌、铁、钙和镁中的一种,易于与硫化物反应,增强脱氧催化剂的抗硫性能。(3)活性稳定。稀土金属铈、镧可调节复合氧化物的酸碱性,有效抑制CO歧化副反应。复合氧化物脱氧催化剂使用温度低,抗硫中毒能力强,积炭副反应少,因而大大提高了复合氧化物脱氧稳定性。该复合氧化物脱氧催化剂在温度80~180℃,空速500~3000 h-1,可将转炉气等富CO气中最高达1.5%的氧气脱至30ppm以下。
具体实施方案
下面结合具体实验方案对本发明做进一步的详细描述。但发明的权利不受下述实施例的限制。以下各实施例中,涉及百分含量时均为质量百分比。
实施例1
将六水硝酸镍116.4g和69.8g五水硝酸锆溶于180ml去离子水,加热至40℃。保持温度为40℃,搅拌加入8%氨水761g,反应完毕,老化3h,然后过滤,洗涤,130℃烘1h,得到复合氧化物前驱体。称取Ce(NO3)3·6H2O 7.58g溶于56ml去离子水,加入到复合氧化物前驱体和47g氧化锌粉的混合物中并研磨均匀,再挤压成型,保湿放置8h后,经80℃干燥5h,再在450℃焙烧5h后即制得所述的复合氧化物脱氧催化剂产品,其中NiO为30% ,ZnO为47% ,CeO2为3% ,ZrO2为20%。堆密度为0.80g/cm3,比表面积45g/m2,孔容0.18ml/g,命名为TO-1催化剂。
实施例2
将硝酸锰107g和69.8g五水硝酸锆溶于200ml去离子水,加热至70℃。保持温度为70℃,搅拌加入20%氨水388g,反应完毕,老化8h,然后过滤,洗涤,90℃烘3h,得到复合氧化物前驱体。称取La(NO3)3·6H2O 7.98g溶于62ml去离子水,加入到复合氧化物前驱体和35.7gγ-Fe2O3粉的混合物中并研磨均匀,再挤压成型,保湿放置12h后,经120℃干燥2h,再在650℃焙烧2h后即制得所述的复合氧化物脱氧催化剂产品,其中MnO2为52% ,Fe2O3为25% ,La2O3为3%,ZrO2为20%。堆密度为1.15g/cm3,比表面积50g/m2,孔容0.20ml/g,命名为TO-2催化剂。
实施例3
将六水硫酸镍112.2g和122.2g五水硝酸锆溶于280ml去离子水,加热至55℃。保持温度为55℃,搅拌加入14%氨水597g,反应完毕,老化5.5h,然后过滤,洗涤,110℃烘2h,得到复合氧化物前驱体。称取Ce(NO3)3·6H2O 20.2g溶于76ml去离子水,加入到复合氧化物前驱体和39.6g石灰的混合物中并研磨均匀,再挤压成型,保湿放置10h后,经100℃干燥3.5h,再在550℃焙烧3.5h后即制得所述的复合氧化物脱氧催化剂产品其中NiO为32% ,CaO为25% ,CeO2为8% ,ZrO2为35%。堆密度为1.10g/cm3,比表面积60g/m2,孔容0.22ml/g,命名为TO-3催化剂。
实施例4
将硫酸锰71.2g和97.7g五水硝酸锆溶于230ml去离子水,加热至60℃。保持温度为60℃,搅拌加入18%氨水481g,反应完毕,老化6h,然后过滤,洗涤,100℃烘1.5h,得到复合氧化物前驱体。称取La(NO3)3·6H2O 15.98g溶于63ml去离子水,加入到复合氧化物前驱体和27g氧化镁粉的混合物中并研磨均匀,再挤压成型,保湿放置9h后,经110℃干燥4h,再在500℃焙烧4h后即制得所述的复合氧化物脱氧催化剂产品,其中MnO2为41% ,MgO为27% ,La2O3为6% ,ZrO2为28%。堆密度为0.90g/cm3,比表面积62g/m2,孔容0.23ml/g,命名为TO-4催化剂。
实施例5
将硝酸锰70g和87.3g五水硝酸锆溶于280ml去离子水,加热至48℃。保持温度为48℃,搅拌加入15%氨水446g,反应完毕,老化6h,然后过滤,洗涤,120℃烘1.5h,得到复合氧化物前驱体。称取La(NO3)3·6H2O 13.32g溶于90ml去离子水,加入到复合氧化物前驱体和49.8g碱式碳酸锌粉的混合物中并研磨均匀,再挤压成型,保湿放置11h后,经90℃干燥3h,再在520℃焙烧4.8h后即制得所述的复合氧化物脱氧催化剂产品,其中MnO2为34% ,ZnO为36% ,La2O3为5% ,ZrO2为25%。堆密度为0.95g/cm3,比表面积75g/m2,孔容0.26ml/g,命名为TO-5催化剂。
实施例6
将六水硫酸镍105.2g和104.7g五水硝酸锆溶于260ml去离子水,加热至65℃。保持温度为65℃,搅拌加入10%氨水840g,反应完毕,老化6h,然后过滤,洗涤,115℃烘2h,得到复合氧化物前驱体。称取Ce(NO3)3·6H2O 8.84g溶于56ml去离子水,加入到复合氧化物前驱体和47g氧化锌粉的混合物中并研磨均匀,再挤压成型,保湿放置8h后,经80℃干燥5h,再在450℃焙烧5h后即制得所述的复合氧化物脱氧催化剂产品,其中NiO为30% ,MgO为37% ,CeO2为3.5% ,ZrO2为30%。堆密度为0.85g/cm3,比表面积55g/m2,孔容0.19ml/g,命名为TO-6催化剂。
对比例
称取35.3g硝酸铜和Ce(NO3)3·6H2O 7.58g溶于60ml去离子水中制得溶液,再取82gγ-Al2O3载体加入此溶液中等体浸渍,放置8h,120烘干后,得现有技术水解催化剂,其中CuO为15% ,CeO2为3% ,命名为TO-D。
实施例7
本实施例为对上述实施例所得的TO系列复合氧化物脱氧催化剂性能评价情况。反应器为不锈钢反应管,原粒度[φ3~4mm×(4~5)mm],装填量30mL,床层高径比1.5。先通N2,缓慢升温。然后切换配有氧气的原料气。气相色谱仪测出口O2,以脱氧精度来表示复合氧化物脱氧催化剂的活性。在入口气体中CO 50%,H2 3%,CO2 25%,O2 1 .5%,N2 20 .5%时,考察催化剂的脱氧活性,结果见表1。
表1.TO系列催化剂的脱氧性能
稳定条件:空速1800 h-1,温度130℃,入口气体中O21.5%,CS220mg/m3,COS 500mg/m3时,考察催化剂抗硫中毒能力,结果见表2。
表2.TO系列催化剂抗硫中毒能力实验
从表1、2可以看出,本发明样低温脱氧活性以及抗硫中毒能力性能远远高于现有技术对比样。
Claims (8)
1.一种复合氧化物脱氧催化剂,其特征在于:所述的复合氧化物脱氧催化剂结构为aAxOy·bGxOy·mDxOy·nZrO2,其中A为过渡金属镍、锰中的一种,G为锌、铁、钙和镁中的一种,D为稀土金属铈、镧中的一种。
2.根据权利要求1所述的复合氧化物脱氧催化剂,其特征在于:以重量百分比计各组分含量:AO为30%~52%, GxOy为25%~47%,DxOy为3%~8%,ZrO2为20~35%。
3.权利要求1或2所述的复合氧化物脱氧催化剂,其特征在于:所述的复合氧化物脱氧催化剂堆密度为0.80~1.15g/cm3,比表面积45~75g/m2,孔容0.18~0.26ml/g。
4.如权利要求1所述的复合氧化物脱氧催化剂的制备方法,其特征在于:该方法包括以下步骤:
(1)称取一定量的镍或锰的硝酸盐或硫酸盐以及硝酸锆共两种盐溶于水中,形成溶液;
(2)将计算量的沉淀剂配成溶液,加入步骤(1)配制的溶液,在一定温度下发生共沉淀反应,然后老化3~8h,得到混合物;
(3)将步骤(2)得到的混合物过滤、洗涤后,在90~130℃烘干1~3h;
(4)将计算量的稀土金属铈、镧中的一种的硝酸盐和一定量的水配成溶液;
(5)将步骤(3)得到的混合物加入一定量的锌、铁、钙和镁中的一种,研磨均匀再添加步骤(4)溶液,搅拌碾压均匀后挤压成型,保湿放置8~12h后,经80~120℃干燥2~5h,再在450~650℃焙烧3~5h后制得复合氧化物脱氧催化剂。
5.根据权利要求4所述的方法,其特征在于:步骤(2)所用的沉淀剂为8~20%的氨水。
6.根据权利要求4所述的方法,其特征在于:步骤(2)共沉淀的温度为40~70℃。
7.根据权利要求4所述的方法,其特征在于:步骤(5)所用锌为氧化锌或碱式碳酸锌;铁为γ-Fe2O3;钙为石灰;镁为氧化镁或氢氧化镁。
8.权利要求1所述的复合氧化物脱氧催化剂的应用,其特征在于:温度80~180℃,空速500~3000 h-1,能将转炉气等富CO气中最高达1.5%的氧气脱至30ppm以下。
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CN110252315A (zh) * | 2019-06-24 | 2019-09-20 | 中国石油化工股份有限公司 | 一种合成气脱氧催化剂及其制备方法与应用 |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104667940A (zh) * | 2013-12-02 | 2015-06-03 | 中国科学院大连化学物理研究所 | 一种煤层气脱氧铈基复合氧化物催化剂的制备方法及应用 |
CN104888798A (zh) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | 一种用于富co气耐硫脱氧的高活性催化剂及其制备方法 |
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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CN104888798A (zh) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | 一种用于富co气耐硫脱氧的高活性催化剂及其制备方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110252313A (zh) * | 2019-06-20 | 2019-09-20 | 武汉科林精细化工有限公司 | 一种宽温干法烟气脱硝剂及其制备方法 |
CN110252315A (zh) * | 2019-06-24 | 2019-09-20 | 中国石油化工股份有限公司 | 一种合成气脱氧催化剂及其制备方法与应用 |
CN110721707A (zh) * | 2019-10-30 | 2020-01-24 | 大连凯特利催化工程技术有限公司 | 一种合成气低温脱氧催化剂及其制备和应用 |
CN110721707B (zh) * | 2019-10-30 | 2022-07-12 | 大连凯特利催化工程技术有限公司 | 一种合成气低温脱氧催化剂及其制备和应用 |
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