CN113578341A - 一种协同nh3与co的脱硝催化剂的制备方法 - Google Patents
一种协同nh3与co的脱硝催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
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- 238000000034 method Methods 0.000 title claims description 6
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
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- 239000002244 precipitate Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
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- 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 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 229920002472 Starch Polymers 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
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- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
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- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- -1 manganese salt Chemical class 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003546 flue gas Substances 0.000 abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
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- 239000000243 solution Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 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
- 238000001914 filtration Methods 0.000 description 4
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
本发明涉及催化剂材料制备及大气污染控制技术领域,特别公开了一种协同NH3与CO的脱硝催化剂的制备方法。本发明以多种可溶性金属盐、丙二醇、造孔剂为原料溶于去离子水中,利用碳酸钠/和氨水作为沉淀剂,通过组分含量及浸渍时的操作参数获得特定比例的金属配比催化剂,以促进活性组分分布,提高催化剂的性能。本发明利用现有脱硝装置,通过烟气中CO还原NOx,利用CO氧化后释放的能力可以用来加热烟气,降低烟气再加热成本,同时作为脱硝还原剂可以减少NH3的喷入量,降低NH3逃逸。该催化剂非常适合我国当前国情,具有广阔的应用前景。
Description
技术领域
本发明涉及催化剂材料制备及大气污染控制技术领域,特别涉及一种协同NH3与CO的脱硝催化剂的制备方法。
背景技术
随着我国经济的持续发展,国民生活质量要求的不断提高,环境污染带来的压力日益增加,氮氧化物作为当前大气污染的主要污染物之一,其治理水平与我国大气环境优劣息息相关。对于烧结等低温烟气,其烟气温度一般在110-150℃,目前的脱硝工艺主要是利用燃煤电站NH3-SCR脱硝技术,而该催化剂最佳反应温度需要350℃左右,为了解决低温下脱硝效率较差的现状,一般是采取升温烟气至180-200℃、加大喷氨量、提高催化剂中V含量等措施,但上述方法中存在多种弊端,如脱硝成本增大,氨逃逸增加等,难以达到烟气排放标准要求。
且随着钢铁企业烧结机一氧化碳限值排放实施,烧结烟气中大量的CO亟需处理,CO不仅是一种污染物,更是一种能源和还原剂,其氧化后释放的能力可以用来加热烟气,降低烟气再加热成本,同时作为脱硝还原剂可以减少NH3的喷入量,降低NH3逃逸。因此开发协同NH3与CO脱硝的催化剂是很有必要的。
发明内容
本发明为了弥补现有技术的不足,提供了一种工艺简单、降低烟气再热成本、节能环保的协同NH3与CO的脱硝催化剂的制备方法。
本发明是通过如下技术方案实现的:
一种协同NH3与CO的脱硝催化剂的制备方法,包括如下步骤:
(1)将可溶性锰盐/和铜盐、可溶性钴盐、其他金属盐和丙二醇、造孔剂溶于去离子水中,加热到30-60℃,充分搅拌;
(2)将碳酸钠溶液/和氨水逐滴加入到步骤(1)的溶液中,保持溶液pH值为7.5-9,连续搅拌1-4小时,促使金属盐沉淀;
(3)过滤步骤(2)所得沉淀物,并用蒸馏水洗涤去除杂质;
(4)将步骤(3)所得固体在50-110℃下干燥12-56小时,并在400-600℃下煅烧1-6小时,煅烧升温速率为2-15℃/min,得到产品催化剂。
本发明以多种可溶性金属盐、丙二醇、造孔剂为原料溶于去离子水中,利用碳酸钠/和氨水作为沉淀剂,通过组分含量及浸渍时的操作参数获得特定比例的金属配比催化剂,以促进活性组分分布,提高催化剂的性能。
本发明利用复合金属相互作用产生的优异低温催化脱硝活性,同时特定比例的金属配比显著提高CO选择性氧化能力,避免有氧气氛下CO首先被氧气氧化,而非被NO氧化,整体脱硝效率达到87-98%,可明显降低NH3喷入量和烟气在加热成本。
本发明的更优技术方案为:
步骤(1)中,可溶性锰盐为硝酸锰、碳酸锰、硫酸锰、醋酸锰和氯化锰中的一种或几种;可溶性铜盐为硝酸铜、碳酸铜和醋酸铜中一种或几种;其他金属盐为其他金属的硝酸盐、醋酸盐或氯化盐中的一种或几种。
优选的,锰元素和钴元素的摩尔比为9:1-1:9,锰元素和铈元素的摩尔比为5:1-1:5,锰元素和其他金属元素的摩尔比为9:1-1:9。
优选的,造孔剂为氧化铝、田青粉、淀粉、PVP、PEG、PVA中的一种或几种;造孔剂的添加量为去离子水质量的5-10%。
优选的,丙二醇液体和固体原料的质量比为1:0.5-1:200。
步骤(3)中,用40-60℃的蒸馏水洗涤沉淀物3-5次。
进一步优选的,蒸馏水的温度为40-50℃
步骤(4)中,干燥温度为50-100℃,干燥时间为24-56小时。
步骤(5)中,煅烧升温速率为2-10℃/min。
本发明采用复合金属相互作用,产生特定晶型的催化剂,具有优异低温催化脱硝活性;特定比例的金属配比显著提高CO选择性氧化能力,可明显降低NH3喷入量和烟气再加热成本。
本发明利用现有脱硝装置,通过烟气中CO还原NOx,利用CO氧化后释放的能力可以用来加热烟气,降低烟气再加热成本,同时作为脱硝还原剂可以减少NH3的喷入量,降低NH3逃逸。该催化剂非常适合我国当前国情,具有广阔的应用前景。
附图说明
下面结合附图对本发明作进一步的说明。
图1为实施例1-3所得催化剂在不同温度下的脱硝效率示意图。
具体实施方式
应该指出,以下详细说明都是示例性的,旨在对本申请提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本申请的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和或“包括”时,其指明存在特征、步骤、操作、器件、组件和或它们的组合。
实施例1:
一种协同NH3与CO的脱硝催化剂制备方法,包括如下步骤:
1)将10g硝酸锰、13g硝酸铈、35g硝酸钴、3g丙二醇和2g田青粉溶于去离子水中,加热到40-45℃,并充分搅拌;
2)将0.125mol/L的Na2CO3逐滴加入到步骤1)的溶液中,保持溶液pH值为7.5-9,连续搅拌2.5-3小时,促使金属盐沉淀;
3)过滤步骤2)所得沉淀物,并用蒸馏水(40-60℃)洗涤,重复3-5次,彻底去除杂质;
4)将步骤3)中所得固体在50℃下干燥48小时,并在500℃下煅烧3小时,升温速率设置为2-15℃/min,得到所需催化剂。
实施例2:
一种协同NH3与CO的脱硝催化剂制备方法,包括如下步骤:
1)将10g醋酸锰、3g硝酸铈、27g氯化钴、1.5g硝酸铜、2g丙二醇和1.5g PVP溶于去离子水中,加热到40-45℃,并充分搅拌;
2)将0.150mol/L的Na2CO3逐滴加入到步骤1)的溶液中,保持溶液pH值为7.5-8.5,连续搅拌3-4小时,促使金属盐沉淀;
3)过滤步骤2)所得沉淀物,并用蒸馏水(40-45℃)洗涤,重复3-5次,彻底去除杂质;
4)将步骤3)中所得固体在70℃下干燥36小时,并在450℃下煅烧3.5小时,升温速率设置为5-10℃/min,得到所需催化剂。
实施例3:
一种协同NH3与CO的脱硝催化剂制备方法,包括如下步骤:
1)将8g醋酸锰、32g氯化钴、2.5g硝酸铜、1.5g丙二醇和2g PEG溶于去离子水中,加热到50-60℃,并充分搅拌;
2)将0.3mol/L的氨水逐滴加入到步骤1)的溶液中,保持溶液pH值为8.0-8.5,连续搅拌2-3小时,促使金属盐沉淀;
3)过滤步骤2)所得沉淀物,并用蒸馏水(40-45℃)洗涤,重复3-5次,彻底去除杂质;
4)将步骤3)中所得固体在80℃下干燥28小时,并在500℃下煅烧3小时,升温速率设置为2-10℃/min,得到所需催化剂。
在采用模拟烟气条件下,对该脱硝催化剂的性能进行评价,以NH3为还原剂,反应条件为:NO 500ppm,O2体积分数为5%,NH3 300ppm,CO 700ppm,N2为平衡气,空速为12,000h-1,在反应温度为100~200℃范围内,实施例1、2和3的脱硝效率如附图1所示。
在上述实施例中,对本发明的最佳实施方式做了描述,很显然,在本发明的发明构思下,仍可做出很多变化。在此,应该说明,在本发明的发明构思下所做出的任何改变都将落入本发明的保护范围内。
Claims (9)
1.一种协同NH3与CO的脱硝催化剂的制备方法,其特征为,包括如下步骤:(1)将可溶性锰盐/和铜盐、可溶性钴盐、其他金属盐和丙二醇、造孔剂溶于去离子水中,加热到30-60℃,充分搅拌;(2)将碳酸钠/和氨水加入到步骤(1)的溶液中,保持溶液pH值为7.5-9,连续搅拌1-4小时,促使金属盐沉淀;(3)过滤步骤(2)所得沉淀物,并用蒸馏水洗涤去除杂质;(4)将步骤(3)所得固体在50-110℃下干燥12-56小时,并在400-600℃下煅烧1-6小时,煅烧升温速率为2-15℃/min,得到产品催化剂。
2.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:步骤(1)中,可溶性锰盐为硝酸锰、碳酸锰、硫酸锰、醋酸锰和氯化锰中的一种或几种;可溶性铜盐为硝酸铜、碳酸铜和醋酸铜中一种或几种;其他金属盐为除锰、铜外其他金属的硝酸盐、醋酸盐或氯化盐中的一种或几种。
3.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,步骤(1)中,锰元素和钴元素的摩尔比为9:1-1:9,锰元素和铈元素的摩尔比为5:1-1:5,锰元素和其他金属元素的摩尔比为9:1-1:9。
4.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:步骤(1)中,造孔剂为氧化铝、田青粉、淀粉、PVP、PEG、PVA中的一种或几种;造孔剂的添加量为去离子水质量的0.5-10%。
5.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:步骤(1)中,丙二醇液体和固体原料的质量比为1:0.5-1:200。
6.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:步骤(3)中,用40-60℃的蒸馏水洗涤沉淀物3-5次。
7.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:步骤(4)中,干燥温度为50-100℃,干燥时间为24-56小时。
8.如权利要求1所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:步骤(5)中,煅烧升温速率为2-10℃/min。
9.如权利要求6所述的协同NH3与CO的脱硝催化剂的制备方法,其特征在于:所述蒸馏水的温度为40-50℃。
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