CN116139690A - 一种炼铁高炉废气处理系统 - Google Patents
一种炼铁高炉废气处理系统 Download PDFInfo
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- CN116139690A CN116139690A CN202310134509.4A CN202310134509A CN116139690A CN 116139690 A CN116139690 A CN 116139690A CN 202310134509 A CN202310134509 A CN 202310134509A CN 116139690 A CN116139690 A CN 116139690A
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- iron
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- 239000002912 waste gas Substances 0.000 title claims abstract description 42
- 238000003723 Smelting Methods 0.000 title claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000428 dust Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 27
- 230000023556 desulfurization Effects 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 239000006104 solid solution Substances 0.000 claims abstract description 8
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 42
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 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 18
- 238000001914 filtration Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 15
- 239000000920 calcium hydroxide Substances 0.000 claims description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- BQCFCWXSRCETDO-UHFFFAOYSA-N [Fe].[Mn].[Cu] Chemical compound [Fe].[Mn].[Cu] BQCFCWXSRCETDO-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229960003151 mercaptamine Drugs 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- -1 sulfhydryl graphene Chemical compound 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003546 flue gas Substances 0.000 abstract description 10
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 239000002341 toxic gas Substances 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 6
- 125000003396 thiol group Chemical class [H]S* 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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Abstract
本发明涉及废气处理技术领域,具体为一种炼铁高炉废气处理系统,包括通过烟道相连接的电除尘器、脱硫单元、布袋除尘器、脱硝单元、负压风机和烟囱;所述脱硝单元内存放有脱硝催化剂,所述脱硝催化剂为核壳结构;其中核体包括巯基化氧化石墨烯和铁锰铜复合氧化物;壳体为过渡金属元素掺杂铈锆固溶体,本系统能够充分处理炼铁高炉废气中的硫氧化物、氮氧化物和其余有毒气体,对于推进钢铁行业烟气超低排放治理具有重要意义。
Description
技术领域
本发明涉及废气处理技术领域,具体为一种炼铁高炉废气处理系统。
背景技术
钢铁工业在我国重化工业中占有举足轻重的地位,而高炉炼铁技术作为其中一项重要技术,产生的废气会造成许多环境问题,炼铁高炉废气所含的污染物主要包括颗粒物、SO2、NOx和二噁英等,推进钢铁行业烟气超低排放治理是推进污染物深度减排的必由之路,对于烧结烟气中的NOx的去除目前以催化还原脱硝法为主,由于小型炼铁高炉废气经脱硫后温度一般低于200℃,不能直接采用SCR技术,还需要对废气进行加热,这无疑会增加成本,其次废气的含湿量和含氧量较大,如果选择的催化剂不具备良好的抗热水性能,也会造成脱硝效果不理想。
发明内容
发明目的:针对上述技术问题,本发明提出了一种炼铁高炉废气处理系统。
所采用的技术方案如下:
一种炼铁高炉废气处理系统,包括通过烟道相连接的电除尘器、脱硫单元、布袋除尘器、脱硝单元、负压风机和烟囱;
所述脱硝单元内存放有脱硝催化剂,所述脱硝催化剂为核壳结构;
其中核体包括巯基化氧化石墨烯和铁锰铜复合氧化物;
壳体为过渡金属元素掺杂铈锆固溶体。
进一步地,还包括吸收液存储单元,用以存储碱性吸收液,所述吸收液存储单元通过管道与所述脱硫单元相连接。
进一步地,还包括消石灰存储单元和活性炭存储单元,所述消石灰存储单元和活性炭存储单元分别通过管道与所述脱硫单元、布袋除尘器之间的烟道相连接。
进一步地,还包括换热器,所述电除尘器、脱硫单元之间的烟道与所述布袋除尘器、脱硝单元之间的烟道间距设置在所述换热器的内部。
进一步地,包括液氨存储单元,用以存储液氨,还包括液氨蒸发器,用以将液氨加热蒸发成为氨气,所述液氨存储单元与液氨蒸发器通过管道与所述布袋除尘器、脱硝单元之间的烟道相连接。
进一步地,所述巯基化氧化石墨烯的制备方法如下:
将氧化石墨烯、巯基乙胺、EDC、DMSO充分混合后40-50℃搅拌反应36-48h,反应结束后过滤,所得固体洗涤后干燥至恒重即可。
进一步地,所述铁锰铜复合氧化物的制备方法如下:
将硫酸亚铁和硫酸铜溶解于水中得到溶液A,将高锰酸钾溶解于水中得到溶液B,在不断搅拌的条件下,将溶液B缓慢滴加到溶液A中,滴毕后,反应30-50min后滴加氢氧化钠溶液至体系pH为9-10,继续搅拌5-10h,再静置陈化5-10h,过滤后洗涤,再干燥至恒重即可。
进一步地,所述脱硝催化剂的制备方法如下:
将巯基化氧化石墨烯和铁锰铜复合氧化物混合球磨造粒,所得颗粒微波加热干燥后分散于水中,再将硝酸铈、硝酸锆、过渡金属元素硝酸盐加入,搅拌均匀后以氨水为沉淀剂,将氨水缓慢滴加到溶液中,当溶液pH至10-11时,停止滴加氨水,继续搅拌30-50min后静置陈化10-15h,过滤、洗涤、干燥,转移至马弗炉中600-650℃焙烧4-8h即可。
进一步地,所述硝酸铈、硝酸锆、过渡金属元素硝酸盐的摩尔比为3-5:1-2:0.05-0.15。
进一步地,所述过渡金属元素硝酸盐为硝酸铬、硝酸钴、硝酸镍、硝酸铜、硝酸锌、硝酸银中的任意一种或多种,优选为硝酸钴。
本发明的有益效果:
本发明提供了一种炼铁高炉废气处理系统,能够充分处理炼铁高炉废气中的粉尘、硫氧化物、氮氧化物和其余有毒气体,通过在系统中加入换热器,有利于炼铁高炉废气的余热回收及热量置换,利用回收的热量对脱硫后的废气再加热,可以提高后续脱硝效果,降低再加热的能源消耗,本发明中所使用的脱硝催化剂在较低温度下也有较好的脱硝性能,以巯基化氧化石墨烯和铁锰铜复合氧化物为核体,以过渡金属元素掺杂铈锆固溶体为壳体,巯基化氧化石墨烯可以提高铁锰铜复合氧化物的机械强度,并改善其吸附性能,有助于其成型造粒,过渡金属元素掺杂铈锆固溶体有助于提高脱硝催化剂的催化性能,优化催化剂的抗热水抗硫及中低温脱硝性能,对于推进钢铁行业烟气超低排放治理具有重要意义。
附图说明
图1为本发明实施例中炼铁高炉废气处理系统的结构示意图;
图中标号分别代表:
1-电除尘器、2-换热器、3-脱硫单元、4-吸收液存储单元、5-消石灰存储单元、6-活性炭存储单元、7-布袋除尘器、8-脱硝单元、9-液氨存储单元、10-负压风机、11-烟囱、12-液氨蒸发器。
具体实施方式
实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。本发明未提及的技术均参照现有技术。
本发明提供了一种炼铁高炉废气处理系统,包括通过烟道相连接的电除尘器、脱硫单元、布袋除尘器、脱硝单元、负压风机和烟囱;
吸收液存储单元,用以存储碱性吸收液,碱性吸收液为氢氧化钠溶液、氢氧化钙溶液或碳酸钠溶液,优选为氢氧化钠溶液,吸收液存储单元通过管道与脱硫单元相连接,炼铁高炉废气经过电除尘器除尘后由脱硫单元的底部进入,吸收液存储单元通过管道向下喷洒碱性吸收液,对炼铁高炉废气中的SO2进行吸收,吸收了SO2的碱性吸收液从脱硫单元底部排除,进行回收处理;
消石灰存储单元和活性炭存储单元,消石灰存储单元和活性炭存储单元分别通过管道与脱硫单元、布袋除尘器之间的烟道相连接,消石灰与活性炭相结合是一种有效治理炼铁高炉废气的方法,用喷射风机将消石灰和活性炭喷入脱硫单元、布袋除尘器之间的烟道中,消石灰与废气中的酸性气体反应将其除去,活性炭因其独有的吸附性能将吸收废气中的二恶英等有毒气体,与消石灰和活性炭反应后的废气带着飞灰和各种粉尘进入布袋除尘器;
换热器,电除尘器、脱硫单元之间的烟道与布袋除尘器、脱硝单元之间的烟道间距设置在换热器的内部,换热器用于废气的余热回收及系统中所必须的热量置换,对脱硫后的废气再加热,提高后续脱硝效果;
液氨存储单元,用以存储液氨;
液氨蒸发器,用以将液氨加热蒸发成为氨气;
液氨存储单元与液氨蒸发器通过管道与所述布袋除尘器、脱硝单元之间的烟道相连接,液氨作为脱硝还原剂,通过管道将液氨存储单元内的液氨送至液氨蒸发器内加热蒸发成为氨气再送至脱硝单元;
上述所有烟道和管道上均设置有阀门;
脱硝单元内存放有脱硝催化剂,脱硝催化剂为核壳结构;
其中核体包括巯基化氧化石墨烯和铁锰铜复合氧化物;
壳体为过渡金属元素掺杂铈锆固溶体。
巯基化氧化石墨烯的制备方法如下:
将氧化石墨烯、巯基乙胺、EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺)、DMSO(二甲基亚砜)充分混合后40-50℃搅拌反应36-48h,反应结束后过滤,所得固体洗涤后干燥至恒重即可。
铁锰铜复合氧化物的制备方法如下:
将硫酸亚铁和硫酸铜溶解于水中得到溶液A,将高锰酸钾和氢氧化钠溶解于水中得到溶液B,在不断搅拌的条件下,将溶液B缓慢滴加到溶液A中.滴毕后,继续搅拌5-10h,再静置陈化5-10h,过滤后洗涤,再干燥至恒重即可。
脱硝催化剂的制备方法如下:
将巯基化氧化石墨烯和铁锰铜复合氧化物混合球磨造粒,所得颗粒微波加热干燥后分散于水中,再将硝酸铈、硝酸锆、过渡金属元素硝酸盐加入,搅拌均匀后以氨水为沉淀剂,将氨水缓慢滴加到溶液中,当溶液pH至10-11时,停止滴加氨水,继续搅拌30-50min后静置陈化10-15h,过滤、洗涤、干燥,转移至马弗炉中600-650℃焙烧4-8h即可。
其中,所述硝酸铈、硝酸锆、过渡金属元素硝酸盐的摩尔比为3-5:1-2:0.05-0.15。
其中,所述过渡金属元素硝酸盐为硝酸铬、硝酸钴、硝酸镍、硝酸铜、硝酸锌、硝酸银中的任意一种或多种,优选为硝酸钴。
本系统的运行流程如下:
炼铁高炉废气经电除尘器除尘后进入换热器与介质进行热交换后由脱硫单元的底部进入,吸收液存储单元通过管道向下喷洒碱性吸收液,对炼铁高炉废气中的SO2进行吸收,喷射风机将消石灰和活性炭喷入脱硫单元、布袋除尘器之间的烟道中,与经过脱硫后的炼铁高炉废气混合对酸性气体和有毒气体进行进一步吸收和反应,与消石灰和活性炭反应后的废气带着飞灰和各种粉尘进入布袋除尘器,经过除尘后的废气与氨气混合进入脱硝单元进行催化还原脱硝,经过脱硝后的废气最后通过烟囱排入大气中。
实施例1:
参考图1,本发明提供了一种炼铁高炉废气处理系统,包括通过烟道相连接的电除尘器(1)、脱硫单元(3)、布袋除尘器(7)、脱硝单元(8)、负压风机(10)和烟囱(11);
吸收液存储单元(4),用以存储0.01mol/L氢氧化钠溶液,吸收液存储单元(4)通过管道与脱硫单元(3)相连接;
消石灰存储单元(5)和活性炭存储单元(6),消石灰存储单元(5)和活性炭存储单元(6)分别通过管道与脱硫单元(3)、布袋除尘器(7)之间的烟道相连接;
换热器(2),电除尘器(1)、脱硫单元(3)之间的烟道与布袋除尘器(7)、脱硝单元(8)之间的烟道间距设置在换热器(2)的内部;
包括液氨存储单元(9),用以存储液氨,还包括液氨蒸发器(12),用以将液氨加热蒸发成为氨气,所述液氨存储单元(9)与液氨蒸发器(12)通过管道与布袋除尘器(7)、脱硝单元(8)之间的烟道相连接。
脱硝单元(8)内存放有脱硝催化剂,脱硝催化剂为核壳结构;
其中核体包括巯基化氧化石墨烯和铁锰铜复合氧化物;
壳体为钴掺杂铈锆固溶体。
脱硝催化剂的制备方法如下:
将10g氧化石墨烯、50g巯基乙胺、25g EDC、500mL DMSO充分混合后45℃搅拌反应48h,反应结束后过滤,所得固体用丙酮和水多次洗涤后50℃干燥至恒重得到巯基化氧化石墨烯,将90.6g硫酸亚铁和48g硫酸铜溶解于500mL水中得到溶液A,将31.6g高锰酸钾溶解于300mL水中得到溶液B,在不断搅拌的条件下,将溶液B缓慢滴加到溶液A中,滴毕后,反应40min后滴加氢氧化钠溶液至体系pH为10,继续搅拌8h,再静置陈化8h,过滤后用丙酮和水交替洗涤,再50℃干燥至恒重得到铁锰铜复合氧化物,将5g巯基化氧化石墨烯和15g铁锰铜复合氧化物混合球磨造粒,所得颗粒微波加热干燥后分散于500mL水中,再将1.45g硝酸铈、10g硝酸锆、0.275g硝酸钴加入,搅拌均匀后以氨水为沉淀剂,将氨水缓慢滴加到溶液中,当溶液pH至11时,停止滴加氨水,继续搅拌40min后静置陈化15h,过滤、用丙酮和水多次洗涤、50℃干燥10h,转移至马弗炉中650℃焙烧5h即可。
实施例2:
与实施例1基本相同,区别在于,脱硝催化剂的制备方法如下:
将10g氧化石墨烯、50g巯基乙胺、25g EDC、500mL DMSO充分混合后50℃搅拌反应48h,反应结束后过滤,所得固体用丙酮和水多次洗涤后50℃干燥至恒重得到巯基化氧化石墨烯,将90.6g硫酸亚铁和48g硫酸铜溶解于500mL水中得到溶液A,将31.6g高锰酸钾溶解于300mL水中得到溶液B,在不断搅拌的条件下,将溶液B缓慢滴加到溶液A中,滴毕后,反应50min后滴加氢氧化钠溶液至体系pH为10,继续搅拌10h,再静置陈化10h,过滤后用丙酮和水交替洗涤,再50℃干燥至恒重得到铁锰铜复合氧化物,将5g巯基化氧化石墨烯和15g铁锰铜复合氧化物混合球磨造粒,所得颗粒微波加热干燥后分散于500mL水中,再将1.45g硝酸铈、10g硝酸锆、0.275g硝酸钴加入,搅拌均匀后以氨水为沉淀剂,将氨水缓慢滴加到溶液中,当溶液pH至11时,停止滴加氨水,继续搅拌50min后静置陈化15h,过滤、用丙酮和水多次洗涤、50℃干燥10h,转移至马弗炉中650℃焙烧8h即可。
实施例3:
与实施例1基本相同,区别在于,脱硝催化剂的制备方法如下:
将10g氧化石墨烯、50g巯基乙胺、25g EDC、500mL DMSO充分混合后40℃搅拌反应36h,反应结束后过滤,所得固体用丙酮和水多次洗涤后50℃干燥至恒重得到巯基化氧化石墨烯,将90.6g硫酸亚铁和48g硫酸铜溶解于500mL水中得到溶液A,将31.6g高锰酸钾溶解于300mL水中得到溶液B,在不断搅拌的条件下,将溶液B缓慢滴加到溶液A中,滴毕后,反应30min后滴加氢氧化钠溶液至体系pH为9,继续搅拌5h,再静置陈化5h,过滤后用丙酮和水交替洗涤,再50℃干燥至恒重得到铁锰铜复合氧化物,将5g巯基化氧化石墨烯和15g铁锰铜复合氧化物混合球磨造粒,所得颗粒微波加热干燥后分散于500mL水中,再将1.45g硝酸铈、10g硝酸锆、0.275g硝酸钴加入,搅拌均匀后以氨水为沉淀剂,将氨水缓慢滴加到溶液中,当溶液pH至10时,停止滴加氨水,继续搅拌30min后静置陈化10h,过滤、用丙酮和水多次洗涤、50℃干燥10h,转移至马弗炉中600℃焙烧4h即可。
实施例4:
与实施例1基本相同,区别在于,将硝酸钴用等物质的量的硝酸镍代替。
实施例5:
与实施例1基本相同,区别在于,将硝酸钴用等物质的量的硝酸锌代替。
对比例1:
与实施例1基本相同,区别在于,壳体为铈锆固溶体,不进行钴掺杂。
对比例2:
与实施例1基本相同,区别在于,脱硝催化剂不含壳体。
对比例3:
与实施例1基本相同,区别在于,用氧化石墨烯代替巯基化氧化石墨烯。
性能测试:
测试在一维石英管固定床实验台上进行,将本发明实施例1-5及对比例1-3中的脱硝催化剂作为试样,利用石英棉两端固定脱硝催化剂于石英管内,模拟烟气气体浓度为:0.5vol%NO、0.5vol%NO2、0.1vol%NH3、5vol%O2,0.5vol%SO2、5vol%H2O、其余为N2,测试过程使用10g脱硝催化剂进行测试,模拟烟气流量为150mL/min,空速比(Gas Hourly SpaceVelocity,GHSV)为12786/h,测试温度为135±10℃,利用德国MRU公司Delta 2000CD-IV型烟气分析仪测量反应段进、出口烟气中NOx浓度;
脱硝效率由以下公式计算
测试结果如下表1所示:
表1:
η1实施例198.5实施例297.9实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 | η1实施例198.5实施例297.9实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 |
实施例198.5实施例297.9实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 | 98.5实施例297.9实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 |
实施例297.9实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 | 97.9实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 |
实施例398.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 | 98.3实施例495.6实施例593.8对比例195.1对比例290.4对比例3 |
实施例495.6实施例593.8对比例195.1对比例290.4对比例3 | 95.6实施例593.8对比例195.1对比例290.4对比例3 |
实施例593.8对比例195.1对比例290.4对比例3 | 93.8对比例195.1对比例290.4对比例3 |
对比例195.1对比例290.4对比例3 | 95.1对比例290.4对比例3 |
对比例290.4对比例3 | 90.4对比例3 |
对比例3 | 94.2 |
由上表1可知,本发明中所使用的脱硝催化剂在较低温度下也有较好的脱硝性能。
以上实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种炼铁高炉废气处理系统,其特征在于,包括通过烟道相连接的电除尘器、脱硫单元、布袋除尘器、脱硝单元、负压风机和烟囱;
所述脱硝单元内存放有脱硝催化剂,所述脱硝催化剂为核壳结构;
其中,核体包括巯基化氧化石墨烯和铁锰铜复合氧化物;
壳体为过渡金属元素掺杂铈锆固溶体。
2.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,还包括吸收液存储单元,用以存储碱性吸收液,所述吸收液存储单元通过管道与所述脱硫单元相连接。
3.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,还包括消石灰存储单元和活性炭存储单元,所述消石灰存储单元和活性炭存储单元分别通过管道与所述脱硫单元、布袋除尘器之间的烟道相连接。
4.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,还包括换热器,所述电除尘器、脱硫单元之间的烟道与所述布袋除尘器、脱硝单元之间的烟道间距设置在所述换热器的内部。
5.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,包括液氨存储单元,用以存储液氨,还包括液氨蒸发器,用以将液氨加热蒸发成为氨气,所述液氨存储单元与液氨蒸发器通过管道与所述布袋除尘器、脱硝单元之间的烟道相连接。
6.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,所述巯基化氧化石墨烯的制备方法如下:
将氧化石墨烯、巯基乙胺、EDC、DMSO充分混合后40-50℃搅拌反应36-48h,反应结束后过滤,所得固体洗涤后干燥至恒重即可。
7.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,所述铁锰铜复合氧化物的制备方法如下:
将硫酸亚铁和硫酸铜溶解于水中得到溶液A,将高锰酸钾溶解于水中得到溶液B,在不断搅拌的条件下,将溶液B缓慢滴加到溶液A中,滴毕后,反应30-50min后滴加氢氧化钠溶液至体系pH为9-10,继续搅拌5-10h,再静置陈化5-10h,过滤后洗涤,再干燥至恒重即可。
8.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,所述脱硝催化剂的制备方法如下:
将巯基化氧化石墨烯和铁锰铜复合氧化物混合球磨造粒,所得颗粒微波加热干燥后分散于水中,再将硝酸铈、硝酸锆、过渡金属元素硝酸盐加入,搅拌均匀后以氨水为沉淀剂,将氨水缓慢滴加到溶液中,当溶液pH至10-11时,停止滴加氨水,继续搅拌30-50min后静置陈化10-15h,过滤、洗涤、干燥,转移至马弗炉中600-650℃焙烧4-8h即可。
9.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,所述硝酸铈、硝酸锆、过渡金属元素硝酸盐的摩尔比为3-5:1-2:0.05-0.15。
10.如权利要求1所述的炼铁高炉废气处理系统,其特征在于,所述过渡金属元素硝酸盐为硝酸铬、硝酸钴、硝酸镍、硝酸铜、硝酸锌、硝酸银中的任意一种或多种,优选为硝酸钴。
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