CN103301863A - 基于钢渣的scr脱硝催化剂及其制备方法 - Google Patents
基于钢渣的scr脱硝催化剂及其制备方法 Download PDFInfo
- Publication number
- CN103301863A CN103301863A CN2013102826083A CN201310282608A CN103301863A CN 103301863 A CN103301863 A CN 103301863A CN 2013102826083 A CN2013102826083 A CN 2013102826083A CN 201310282608 A CN201310282608 A CN 201310282608A CN 103301863 A CN103301863 A CN 103301863A
- Authority
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- Prior art keywords
- catalyst
- slag
- scr
- pickling
- flue gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002893 slag Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010531 catalytic reduction reaction Methods 0.000 title abstract description 3
- 238000005554 pickling Methods 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound 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[O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003546 flue gas Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical group 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[Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound 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[Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound 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O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 11
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials 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[Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 10
- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Inorganic materials 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[Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 claims description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 10
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials 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[O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002242 deionisation method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000003638 reducing agent Substances 0.000 claims description 4
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[S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound 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NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910015621 MoO Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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Abstract
一种用于烟气脱硝催化技术领域的基于钢渣的SCR脱硝催化剂及其制备方法,通过以固体冶金钢渣为原料,经酸洗干燥后制成;得到的催化剂的表面积为4.8174~54.6885m2/g,平均孔径在64-110nm。本发明无需通过浸渍法添加活性组分,从而简化了制备工艺;制备得到的催化剂能在150-250°C达到较高的NO脱除率。
Description
基于钢渣的SCR脱硝催化剂及其制备方法
技术领域
[0001] 本发明涉及的是一种用于烟气脱硝催化技术领域的方法,具体是一种基于钢渣的SCR脱硝催化剂及其制备方法。
背景技术
[0002] 氮氧化物是主要的大气污染物之一。据有关部门统计,2010年中国NOx排放量为1852万吨,比2006年增长了 22%,而我国以煤炭为主的能源结构导致氮氧化物的排放总量长期居高不下。同时2011年新颁布的《火电厂大气污染物排放标准》(GB13223-2011)已开始实施,要求新建机组从2012年I月I日开始、现有机组从2014年7月I日开始执行100mg/Nm3的氮氧化物污染物排放限值。所以控制氮氧化物的排放已成为“十二五”环境保护工作的重中之重。要使烟气达到愈加严格的排放标准,在通过烟气再循环、分段送风、再燃烧技术、低NOx燃烧等技术控制燃烧过程中NOx生成的基础上,还需采用燃烧后脱硝技术。燃烧后脱硝技术中的选择性催化还原(Selective Catalytic Reduction, SCR)技术是目前脱硝效果最好的成熟技术,脱硝效率可达90%以上。
[0003] SCR技术是指还原剂(NH3、尿素)在金属催化剂作用下,选择性地与NOx反应生成N2和H2O,该技术的核心是催化剂。现有的SCR催化剂可分为三类:贵金属催化剂、分子筛催化剂和金属氧化物催化剂。贵金属催化剂造价昂贵,易发生氧抑制和硫中毒;分子筛催化剂的催化活性主要表现在中高温区,实际应用中存在水抑制及硫中毒问题;过渡金属氧化物负载型催化剂在富氧条件下、以NH3为还原剂的SCR反应中表现出了较好的催化活性,应用普遍的是以TiO2为载体的V205/W03及MoO3催化剂。
[0004] 然而,目前掌握SCR催化剂生产技术的主要是国外几家公司,如丹麦托普索、日本触媒化成等。国内的催化剂生产厂商也只是引进国外的技术,SCR催化剂生产技术尚未能实现国产化,并且SCR催化剂制造成本高,也阻碍了其广泛的应用。因此,寻求廉价的SCR催化剂成为必要。
发明内容
[0005] 本发明针对现有技术存在的上述不足,提出一种基于钢渣的SCR脱硝催化剂及其制备方法,固体钢渣为原料,通过简单工艺将其中的活性成分活化,就可得到新型的脱硝催化剂,无需通过浸溃法添加活性组分,从而简化了制备工艺;制备得到的催化剂能在150-250° C达到较高的NO脱除率。
[0006] 本发明是通过以下技术方案实现的:
[0007] 本发明涉及一种基于钢渣的SCR脱硝催化剂,该催化剂中各组分的质量比为CaO =Fe2O3:Si02:MgO:MnO =Al2O3:Ti02 =V2O5 =Cr2O3 =P2O5:SrO:S03:NbO= 1:(1.6 〜4.9):(0.8 〜1.6): (0.3 〜0.5): (0.1 〜0.5): (0.06 〜0.08): (0.03 〜0.04): (0.0009 〜
0.009):(0.01 〜0.07):(0.05 〜0.09): (0 〜0.0007):(0.007 〜0.03):(0.0007 〜
0.003)。[0008] 所述的催化剂的表面积为4.8174〜54.6885m2/g,平均孔径在64_110nm。
[0009] 本发明涉及上述催化剂的制备方法,以固体冶金钢渣为原料,经酸洗干燥后制成。
[0010] 所述的固体冶金钢渣富含金属组分,其主要成分是CaO、Fe2O3、SiO2,同时还含有一定量的Mg、Mn、Al、Fe、Ti等金属活性成分。
[0011] 所述的固体冶金钢渣经破碎、筛分处理,其粒径为0.25〜2mm。
[0012] 所述的酸洗是指:在70_90°C恒温水浴中用硝酸酸洗lh,其中:硝酸:固体冶金钢渣=5mL: lg,酸洗后再用去离子反复水洗至中性。
[0013] 所述的干燥是指:置于马弗炉内200-400°C下干燥3h。
[0014] 所述的酸洗温度为70° C,干燥温度为400° C。
[0015] 本发明涉及一种上述催化剂的用途,将该催化剂用于烟气脱硝的SCR催化剂。
[0016] 所述的烟气脱硝以NH3为还原剂,反应在150-250° C之间进行。
[0017] 所述的烟气中存在500ppm以上的NO,脱硝效率在78-84%以上。
技术效果
[0018] 与现有技术相比,本发明的催化剂廉价、制作工艺简单,同时降低了 SCR的反应温度,使得SCR工艺既高效 又经济,很符合我国现有国情。
具体实施方式
[0019] 下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1
[0020] 本实施例包括以下步骤:
[0021 ]先将 CaO、Fe2O3' Si02、MgO、MnO、Al2O3' Ti02、V205、Cr203、P2O5> SrO, SO3> NbO, K2O, Cl,含量相应为 49.7483%、26.1204%、9.8934%、6.8268%、3.0459%、1.6362%、0.5501%、0.1599%、
0.1941%、1.6147%、0.0297%,0.1357%、0.0146%、0.0074%,0.0227% 的转炉钢渣破碎、筛分,称取0.25-0.8臟粒径的钢渣2(^,按照酸:渣=51^: Ig的比例将废渣溶于硝酸中,将烧瓶置于70°C的水浴中加热lh,间歇搅拌;酸洗后,从硝酸中将钢渣过滤出来,再用去离子反复水洗直至中性;最后将其置于马弗炉内400°C干燥3h,即得所需要的催化剂。
[0022] 本实施例制备得到的催化剂的组分为:Ca0、Fe203、Si02、Mg0、Mn0、Al203、Ti02、V205、Cr2O3> P205、SrO, SO3> NbO,含量对应为 24.0067%, 39.1908%, 20.1752%, 7.7951%, 3.824%、
1.49%,0.8529%,0.2165%、0.2594%、1.97%,0.0148%、0.1864%,0.0183% ;该催化剂的表面积为54.6885m2/g,平均孔径在82nm左右。催化剂在NO体积浓度为500ppm、温度为150° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾' NO的脱除率为91% ;在NO体积浓度为500ppm、温度为200° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾' NO的脱除率为98% ;在NO体积浓度为500ppm、温度为250° C、O2浓度为5%、NH3/N0=1.0情况下,空速为7700^1, NO的脱除率为88%。
实施例2
[0023] 本实施例包括以下步骤:
[0024]先将组分 CaO、Fe2O3' SiO2' Mg。、Mn。、Al2O3' TiO2' V205、Cr2O3> P205、SrO, SO3> Nb。、K2O, Cl,含量相应为 49.7483%,26.1204%,9.8934%,6.8268%,3.0459%、1.6362%,0.5501%、
0.1599%、0.1941%、1.6147%、0.0297%,0.1357%、0.0146%、0.0074%,0.0227% 的转炉钢渣破碎、筛分,称取0.25-0.8mm粒径的钢渣20g,按照酸:渣=5mL: Ig的比例将钢渣溶于硝酸中,将烧瓶置于70°C的水浴中加热lh,间歇搅拌;酸洗后,从硝酸中将钢渣过滤出来,再用去离子反复水洗直至中性;最后将其置于马弗炉内300°C干燥3h,即得所需要的催化剂。
[0025] 本实施例制备得到的催化剂的组分为:Ca0、Fe203、Si02、Mg0、Mn0、Al203、Ti02、V205、Cr2O3> P205、SrO, SO3> NbO,含量对应为 24.0067%, 39.1908%, 20.1752%, 7.7951%, 3.824%、
1.49%,0.8529%,0.2165%、0.2594%、1.97%,0.0148%、0.1864%,0.0183% ;该催化剂的表面积为4.9987m2/g,平均孔径在IlOnm左右。催化剂在NO体积浓度为500ppm、温度为150° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾' NO的脱除率为89% ;在NO体积浓度为500ppm、温度为200° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾' NO的脱除率为97% ;在NO体积浓度为500ppm、温度为250° C、O2浓度为5%、NH3/N0=1.0情况下,空速为7700^1, NO的脱除率为84%。
实施例3
[0026] 本实施例包括以下步骤:
[0027]先将组分为 CaO、Fe2O3' Si02、MgO、Mn。、Al2O3' TiO2' V205、Cr2O3> P205、SrO, SO3> NbO,含量相应为 35.3776%、42.6639%、9.3081%、3.94%、4.0742%、2.2327%、0.4202%、0.1254%、0.6681%、0.8868%,0.0305%,0.2444%,0.028% 的电炉钢渣破碎、筛分,称取 0.8-1.44mm 粒径的钢渣20g,按照酸:渣=5mL: Ig的比例将钢渣溶于硝酸中,将烧瓶置于70°C的水浴中加热lh,间歇搅拌;酸洗后,从硝酸中将钢渣过滤出来,再用去离子反复水洗直至中性;最后将其置于马弗炉内200°C干燥3h,即得所需要的催化剂。
0028] 本实施例制备得到的催化剂的组分为:CaO、Fe203、SiO2, MgO、MnO, A1203、TiO2,V205、Cr2O3, P205、SO3, NbO,含量相应为 11.7546%,56.6003%、18.0165%,4.8536%,5.6022%、
0.8918%、0.3875%、0.0984%、0.7832%、0.6502%、0.3334%、0.0283% ;该催化剂的表面积为
4.8174m2/g,平均孔径在72nm左右。催化剂在NO体积浓度为500ppm、温度为150° C、02浓度为5%、NH3/N0=1.0情况下,空速为770(¾'NO的脱除率为79% ;在NO体积浓度为500ppm、温度为200° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾' NO的脱除率为85% ;在NO体积浓度为500ppm、温度为250° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾'NO的脱除率为78%。
实施例4
[0029] 本实施例包括以下步骤:
[0030]先将组分为 CaO、Fe2O3' Si02、MgO、Mn。、Al2O3' TiO2' V205、Cr2O3> P205、SrO, SO3> NbO,含量相应为 35.3776%、42.6639%、9.3081%、3.94%、4.0742%、2.2327%、0.4202%、0.1254%、
0.6681%、0.8868%、0.0305%、0.2444%、0.028% 的电炉钢渣破碎、筛分,称取 1.44_2mm 粒径的钢渣20g,按照酸:渣=5mL: Ig的比例将钢渣溶于硝酸中,将烧瓶置于70°C的水浴中加热lh,间歇搅拌;酸洗后,从硝酸中将钢渣过滤出来,再用去离子反复水洗直至中性;最后将其置于马弗炉内400°C干燥3h,即得所需要的催化剂。
[0031] 本实施例制备得到的催化剂的组分为:CaO、Fe203、SiO2, MgO、MnO, A1203、TiO2,V205、Cr2O3, P205、SO3, NbO,含量相应为 11.7546%,56.6003%、18.0165%,4.8536%,5.6022%、0.8918%、0.3875%、0.0984%、0.7832%、0.6502%、0.3334%、0.0283% ;该催化剂的表面积为25.9057m2/g,平均孔径在64nm左右。催化剂在NO体积浓度为500ppm、温度为150° (:、02浓度为5%、NH3/NO=l.0情况下,空速为770(¾'NO的脱除率为77% ;在NO体积浓度为500ppm、温度为200° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾' NO的脱除率为89% ;在NO体积浓度为500ppm、温度为250° C、O2浓度为5%、NH3/N0=1.0情况下,空速为770(¾'NO的脱除率为92%。·
Claims (10)
1.一种基于钢渣的SCR脱硝催化剂,其特征在于,其组分的质量比为CaO =Fe2O3 =SiO2:MgO:MnO =Al2O3:Ti02 =V2O5 =Cr2O3:P205:SrO:S03:NbO= 1: (1.6 〜4.9): (0.8 〜1.6): (0.3 〜0.5): (0.1 〜0.5): (0.06 〜0.08): (0.03 〜0.04): (0.0009 〜0.009): (0.01 〜0.07):(0.05 〜0.09): (0 〜0.0007): (0.007 〜0.03): (0.0007 〜0.003)。
2.根据权利要求1所述的催化剂,其特征是,所述的催化剂的表面积为4.8174〜54.6885m2/g,平均孔径在 64_110nm。
3.根据权利要求1或2所述催化剂的应用,其特征在于,用作烟气脱硝的SCR催化剂。
4.根据权利要求3所述的应用,其特征是,所述的烟气脱硝以NH3为还原剂,反应在150-250° C之间进行。
5.根据权利要求3所述的应用,其特征是,所述的烟气中存在500ppm以上的NO,脱硝效率在78-84%以上。
6.一种根据上述任一权利要求所述催化剂的制备方法,其特征在于,以固体冶金钢渣为原料,经酸洗干燥后制成; 所述的固体冶金钢渣富含金属组分,其主要成分是Ca0、Fe203、SiO2,同时还含有一定量的Mg、Mn、Al、Fe、Ti等金属活性成分。
7.根据权利要求6所述的方法,其特征是,所述的固体冶金钢渣经破碎、筛分处理,其粒径为0.25〜2_。
8.根据权利要求6所述的方法,其特征是,所述的酸洗是指:在70-90°C恒温水浴中用硝酸酸洗lh,其中:硝酸:固体冶金钢渣=5mL: lg,酸洗后再用去离子反复水洗至中性。
9.根据权利要求6所述的方法,其特征是,所述的干燥是指:置于马弗炉内200-400°C下干燥3h。
10.根据权利要求6所述的方法,其特征是,所述的酸洗温度为70° C,干燥温度为400。 Co
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