CN111036310A - 一种再生整体式分子筛基脱硝催化剂、其再生方法及应用 - Google Patents
一种再生整体式分子筛基脱硝催化剂、其再生方法及应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 76
- 238000011069 regeneration method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000012266 salt solution Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 13
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 10
- 230000008929 regeneration Effects 0.000 claims abstract description 7
- 238000007664 blowing Methods 0.000 claims abstract description 5
- 239000004071 soot Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 27
- 238000002791 soaking Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002482 Cu–Ni Inorganic materials 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 150000001340 alkali metals Chemical class 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 3
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 206010027439 Metal poisoning Diseases 0.000 abstract description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000010926 purge Methods 0.000 description 6
- 206010008428 Chemical poisoning Diseases 0.000 description 4
- 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 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 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 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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Abstract
本发明属于环保技术和脱硝催化剂再生领域，尤其涉及一种再生整体式分子筛基脱硝催化剂、其再生方法及应用。本发明中，经步骤(1)的吹灰和水洗，能够除去失活的整体式分子筛基脱硝催化剂表面的灰尘和硫铵盐等水溶性盐类；经步骤(2)的铵盐溶液清洗，能够有效去除导致催化剂失活的碱金属、碱土金属、砷、铅等金属中毒物质；经步骤(3)的再负载，使活性金属能够重新负载到分子筛上；从而恢复催化剂的比表面积、表面酸性和脱硝活性，再生催化剂的活性可以恢复至新鲜催化剂的95％以上。本发明能够对整体式分子筛基脱硝催化剂进行有效的清洗和再生，不对分子筛的孔道结构造成破坏，使价格昂贵的分子筛循环利用，且使用中不会产生环境污染。
Description
技术领域
本发明属于环保技术和脱硝催化剂再生领域，尤其涉及一种再生整体式分子筛基脱硝催化剂、其再生方法及应用。
背景技术
近些年，随着国内对氮氧化物污染的重视和相关法律法规的出台及实施，我国对氮氧化物的排放标准越来越严格，NH3-SCR(氨选择性催化还原)是烟气氮氧化物净化技术中最为成熟有效的技术之一，广泛应用于燃煤电厂、工业锅炉、汽车尾气脱硝等，SCR脱硝催化剂是NH3-SCR***最核心的部分，其性能直接影响***的整体脱硝效率和稳定性，是脱硝项目成败的关键。目前，随着大量SCR脱硝催化剂的投入使用，废弃或失活脱硝催化剂将成为该领域的重大固废处理难题。通过对废脱硝催化剂进行再生，可提高或者恢复废脱硝催化剂的活性，使其能够循环使用。
脱硝催化剂中毒失活分为物理中毒和化学中毒。物理中毒主要是硫铵盐覆盖活性位和孔道堵塞造成脱硝催化剂性能下降。化学中毒主要是碱金属(如Na、K等)、碱土金属(如Ca、Mg等)、重金属(如As、Pb等)等金属元素与催化剂的活性位发生结合，占据活性位的同时中和催化剂表面的酸性，影响还原剂NH3的吸附。化学中毒以碱金属的毒害作用最大，是脱硝催化剂失活的主要原因。
SCR脱硝催化剂包括传统钒钨钛催化剂和分子筛基脱硝催化剂。关于传统钒钨钛催化剂的再生方法报道较多，公开号CN102974404A和CN108187763A采用酸性溶液清洗毒害物质，然后用偏钒酸铵、仲钨酸铵混合溶液浸渍补充催化剂活性组分。而分子筛基脱硝催化剂的再生方法报道较少，用酸性溶液清洗会造成脱铝现象或分子筛结构破坏，不适用于分子筛基脱硝催化剂的再生。专利CN108295891A公布了利用还原性气体降低(NH4)2SO4和CuSO4的分解温度，清除Cu基分子筛催化剂表面的硫物种，但不能解决分子筛基脱硝催化剂的碱金属、碱土金属、重金属等化学中毒。
分子筛脱硝催化剂具有较宽的活性温度区间、优良的热稳定性和抗硫性，且催化剂本身具有无毒环保优势，具有良好的环境效益。但分子筛成本较高，分子筛基脱硝催化剂价格昂贵，研究分子筛脱硝催化剂的再生，使分子筛能够循环利用具有重要的商业价值。
发明内容
本发明所要解决的技术问题是，提供一种再生整体式分子筛基脱硝催化剂、其再生方法及应用。
本发明解决上述技术问题的技术方案如下：一种整体式分子筛基脱硝催化剂的再生方法，步骤如下：
(1)将失活的整体式分子筛基脱硝催化剂经过吹灰和水洗处理；
(2)将步骤(1)水洗后的失活整体式分子筛基脱硝催化剂加入至铵盐溶液中，在15-40℃条件下超声铵洗2-5h；
(3)取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入活性金属盐溶液中，在60-100℃条件下浸渍2-12h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂经干燥、焙烧，得再生整体式分子筛基脱硝催化剂。
进一步，所述的整体式分子筛基脱硝催化剂为蜂窝式、平板式或波纹板式分子筛基脱硝催化剂；所述的失活的整体式分子筛基脱硝催化剂为脱硝效率损失30％-70％的整体式分子筛基脱硝催化剂；所述的整体式分子筛基脱硝催化剂的活性组分为分子筛脱硝催化剂。
更进一步，所述的分子筛脱硝催化剂为Cu/ZSM-5、Fe/Beta、Mn/SAPO-34、Co/SSZ-13、Ce/SSZ-39、Cu-Ni/ZSM-5或Mn-Fe/SSZ-13。
进一步，所述铵盐溶液的浓度为1-40wt％；所述铵盐溶液为碳酸氢铵溶液、碳酸铵溶液、氯化铵溶液或硝酸铵溶液。
进一步，步骤(2)中所述铵盐溶液与步骤(1)中所述失活的整体式分子筛基脱硝催化剂的体积比为(5-100):1。
进一步，步骤(3)中所述活性金属盐溶液与步骤(1)中所述整体式分子筛基脱硝催化剂的体积比为(3-100:1)。
进一步，所述的活性金属盐溶液为含有活性金属的醋酸盐溶液、硝酸盐溶液或硫酸盐溶液，浓度为1-50g/L。
更进一步，所述的活性金属为Cu、Fe、Mn、Ni、Co或Ce中的一种或两种以上。
进一步，步骤(4)中，所述的干燥为100-120℃条件下干燥3-6h，所述的焙烧为500-600℃条件下焙烧3-5h。
本发明的第二个目的在于提供一种利用上述再生方法制得的再生整体式分子筛基脱硝催化剂。
本发明的第三个目的在于提供上述再生整体式分子筛基脱硝催化剂在移动源脱硝或固定源脱硝中的应用。
其中，所述移动源脱硝包括机动车、船舶的尾气脱硝过程；所述固定源脱硝包括电厂、锅炉与工厂尾气脱硝过程。
本发明的特点和有益效果是：
(1)本发明中，经过步骤(1)的吹灰和水洗，能够除去失活的整体式分子筛基脱硝催化剂表面的灰尘和硫铵盐等水溶性盐类；经过步骤(2)的铵盐溶液清洗，能够有效去除导致催化剂失活的碱金属、碱土金属、砷、铅等金属中毒物质；经过步骤(3)的再负载，使活性金属能够重新负载到分子筛上；从而恢复催化剂的比表面积、表面酸性和脱硝活性，再生催化剂的活性可以恢复至新鲜催化剂的95％以上。
(2)本发明能够对整体式分子筛基脱硝催化剂进行有效的清洗和再生，不对分子筛的孔道结构造成破坏，使价格昂贵的分子筛循环利用，且使用过程中不会产生环境污染。
附图说明
图1为蜂窝式新鲜Cu/ZSM-5、蜂窝式失活Cu/ZSM-5和实施例1所得蜂窝式再生Cu/ZSM-5的脱硝效率测试结果折线图；
图2为蜂窝式新鲜Cu-Ni/ZSM-5、蜂窝式失活Cu-Ni/ZSM-5和实施例6所得蜂窝式再生Cu-Ni/ZSM-5的脱硝效率测试结果折线图；
图3为波纹板式新鲜Mn-Fe/SSZ-13、波纹板式失活Mn-Fe/SSZ-13和实施例7所得波纹板式再生Mn-Fe/SSZ-13的脱硝效率测试结果折线图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
一种Cu/ZSM-5蜂窝式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Cu/ZSM-5蜂窝式脱硝催化剂(150×150×1000mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活蜂窝式脱硝催化剂加入至200L、5wt％氯化铵溶液中，在25℃条件下超声铵洗5h；
(3)将1.5kg乙酸铜溶解于100L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入乙酸铜溶液中，在80℃条件下浸渍4h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入100℃烘箱中干燥6h，再放入焙烧炉中500℃焙烧5h，得再生的Cu/ZSM-5蜂窝式脱硝催化剂。
实施例2
一种Fe/Beta蜂窝式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Fe/Beta蜂窝式脱硝催化剂(150×150×300mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活蜂窝式脱硝催化剂加入至500L、1wt％氯化铵溶液中，在15℃条件下超声铵洗5h；
(3)将2kg硫酸亚铁溶解于100L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入硫酸亚铁溶液中，在60℃条件下浸渍12h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入120℃烘箱中干燥6h，再放入焙烧炉中600℃焙烧3h，得再生的Fe/Beta蜂窝式脱硝催化剂。
实施例3
一种Mn/SAPO-34波纹板式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Mn/SAPO-34波纹板式脱硝催化剂(150×150×400mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活波纹板式脱硝催化剂加入至200L、40wt％氯化铵溶液中，在40℃条件下超声铵洗2h；
(3)将5kg硫酸锰溶解于200L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入硫酸锰溶液中，在100℃条件下浸渍4h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入110℃烘箱中干燥5h，再放入焙烧炉中500℃焙烧5h，得再生的Mn/SAPO-34波纹板式脱硝催化剂。
实施例4
一种Co/SSZ-13蜂窝式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Co/SSZ-13蜂窝式脱硝催化剂(150×150×1500mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活蜂窝式脱硝催化剂加入至200L、5wt％碳酸氢铵溶液中，在15℃条件下超声铵洗5h；
(3)将5kg硫酸钴溶解于1000L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入硫酸钴溶液中，在70℃条件下浸渍6h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入120℃烘箱中干燥3h，再放入焙烧炉中500℃焙烧5h，得再生的Co/SSZ-13蜂窝式脱硝催化剂。
实施例5
一种Ce/SSZ-39平板式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Ce/SSZ-39平板式脱硝催化剂(150×150×1000mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活平板式脱硝催化剂加入至200L、5wt％碳酸氢铵溶液中，在25℃条件下超声铵洗5h；
(3)将1kg硝酸铈溶解于100L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入硝酸铈溶液中，在80℃条件下浸渍6h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入120℃烘箱中干燥3h，再放入焙烧炉中600℃焙烧3h，得再生的Ce/SSZ-39平板式脱硝催化剂。
实施例6
一种Cu-Ni/ZSM-5蜂窝式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Cu-Ni/ZSM-5蜂窝式脱硝催化剂(150×150×1000mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活蜂窝式脱硝催化剂加入至200L、15wt％碳酸氢铵溶液中，在25℃条件下超声铵洗4h；
(3)将1kg乙酸铜和1.5kg乙酸镍溶解于1000L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入乙酸铜和乙酸镍混合溶液中，在60℃条件下浸渍12h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入110℃烘箱中干燥3h，再放入焙烧炉中600℃焙烧3h，得再生的Cu-Ni/ZSM-5蜂窝式脱硝催化剂。
实施例7
一种Mn-Fe/SSZ-13波纹板式脱硝催化剂的再生方法，步骤如下：
(1)取一根失活的Mn-Fe/SSZ-13波纹板式脱硝催化剂(150×150×500mm)，用0.2MPa无油压缩空气吹扫60min；将吹扫后的催化剂浸泡在100L的清水中，超声清洗2h；
(2)将步骤(1)水洗后的失活波纹板式脱硝催化剂加入至300L、5wt％碳酸氢铵溶液中，在25℃条件下超声铵洗5h；
(3)将2kg硝酸锰和1kg硝酸铁溶解于1000L去离子水中，取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入硝酸锰和硝酸铁混合溶液中，在80℃条件下浸渍8h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂放入100℃烘箱中干燥6h，再放入焙烧炉中550℃焙烧4h，得再生的Mn-Fe/SSZ-13波纹板式脱硝催化剂。
对实施例1、6、7所得催化剂分别进行脱硝效率的活性测试，见图1、图2和图3。
活性测试条件如下：500ppm的一氧化氮，500ppm的氨气，500ppm的二氧化硫，10％的水蒸气，10％的氧气，反应平衡气为氮气，反应空速为10,000h-1。
从图1可以看出，在同时通入硫和水的测试条件下，失活Cu/ZSM-5的脱硝效率与新鲜Cu/ZSM-5相差较大，再生Cu/ZSM-5的脱硝效率与新鲜样品相近；其中，320℃时新鲜Cu/ZSM-5的脱硝效率为98.1％，失活Cu/ZSM-5的脱硝效率为31.8％，再生后Cu/ZSM-5的脱硝效率恢复至97.5％，再生Cu/ZSM-5的脱硝效率恢复至新鲜样品的99.4％，说明本发明的再生工艺对Cu/ZSM-5整体式脱硝催化剂再生效果较好。
从图2、图3可以看出，再生Cu-Ni/ZSM-5的脱硝效率恢复至新鲜样品的96.8％；再生Mn-Fe/SSZ-13的脱硝效率恢复至新鲜样品的96.6％。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种整体式分子筛基脱硝催化剂的再生方法，其特征在于，步骤如下：
(1)将失活的整体式分子筛基脱硝催化剂经过吹灰和水洗处理；
(2)将步骤(1)水洗后的失活整体式分子筛基脱硝催化剂加入至铵盐溶液中，在15-40℃条件下超声铵洗2-5h；
(3)取步骤(2)铵洗后的整体式分子筛基脱硝催化剂放入活性金属盐溶液中，在60-100℃条件下浸渍2-12h，进行活性金属再负载；
(4)将步骤(3)所得整体式分子筛基脱硝催化剂经干燥、焙烧，得再生整体式分子筛基脱硝催化剂。
2.根据权利要求1所述的再生方法，其特征在于，所述的整体式分子筛基脱硝催化剂为蜂窝式、平板式或波纹板式分子筛基脱硝催化剂；所述的失活的整体式分子筛基脱硝催化剂为脱硝效率损失30％-70％的整体式分子筛基脱硝催化剂；所述的整体式分子筛基脱硝催化剂的活性组分为分子筛脱硝催化剂。
3.根据权利要求2所述的再生方法，其特征在于，所述的分子筛脱硝催化剂为Cu/ZSM-5、Fe/Beta、Mn/SAPO-34、Co/SSZ-13、Ce/SSZ-39、Cu-Ni/ZSM-5或Mn-Fe/SSZ-13。
4.根据权利要求1所述的再生方法，其特征在于，所述铵盐溶液的浓度为1-40wt％；所述铵盐溶液为碳酸氢铵溶液、碳酸铵溶液、氯化铵溶液或硝酸铵溶液；步骤(2)中所述铵盐溶液与步骤(1)中所述失活的整体式分子筛基脱硝催化剂的体积比为(5-100):1。
5.根据权利要求1所述的再生方法，其特征在于，步骤(3)中所述活性金属盐溶液与步骤(1)中所述整体式分子筛基脱硝催化剂的体积比为(3-100:1)。
6.根据权利要求1所述的再生方法，其特征在于，所述的活性金属盐溶液为含有活性金属的醋酸盐溶液、硝酸盐溶液或硫酸盐溶液，浓度为1-50g/L。
7.根据权利要求6所述的再生方法，其特征在于，所述的活性金属为Cu、Fe、Mn、Ni、Co或Ce中的一种或两种以上。
8.根据权利要求1所述的再生方法，其特征在于，步骤(4)中，所述的干燥为100-120℃条件下干燥3-6h，所述的焙烧为500-600℃条件下焙烧3-5h。
9.一种利用权利要求1所述的整体式分子筛基脱硝催化剂的再生方法制得的再生整体式分子筛基脱硝催化剂。
10.一种权利要求9所述再生整体式分子筛基脱硝催化剂在移动源脱硝或固定源脱硝中的应用。
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