CN109569643A - 一种负载型常温除臭氧催化剂的制备方法 - Google Patents
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
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- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
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- 238000009938 salting Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
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- 238000002156 mixing Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000007792 addition Methods 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000000149 penetrating effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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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- B01D—SEPARATION
- 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
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Abstract
本发明公开了一种负载型常温除臭氧催化剂的制备方法，特点是包括以下步骤：(1)将含有沉淀剂的溶液匀速滴加于含有铜、锰金属盐溶液中，滴加完毕后继续搅拌2‑5小时，将得到的沉淀抽滤、洗涤干燥后，在350‑500℃空气气氛中焙烧2‑3小时，得到除臭氧催化剂活性粉体；(2)将步骤(1)得到的活性粉体、去离子水与粘结剂按质量比(2‑3)：(13‑15)(3‑4)的比例混合，并搅拌3‑5小时得到浸渍液，将蜂窝状载体浸渍在浸渍液中0.5‑1min后，吹去残液，在100‑140℃条件下烘干，得到负载型常温除臭氧催化剂，优点是除臭氧率高、环保无污染。
Description
技术领域
本发明涉及一种除臭氧催化剂，尤其是涉及一种负载型常温除臭氧催化剂的制备方法。
背景技术
臭氧是氧气的同素异形体，是一种不稳定的具有刺激性气味的淡紫色气体，由于臭氧具有较强的氧化性而被广泛应用于工业水的处理，烟气的脱硫脱硝处理，但是在尾气中含有大量的未分解的臭氧；而且家用电器中例如空调、电视等在使用过程中也会释放出少量的臭氧；此外，夏季高温时，空气中的氧气在太阳光的照射下会经过复杂的反应转变成臭氧，这些臭氧在空气中会对人体健康造成极大的伤害。中华人民共和国空气质量标准对室内外环境中臭氧的浓度做了规定：室内臭氧浓度不得超过0.08ppm，室外臭氧浓度不得超过0.1ppm。所以，对空气中的臭氧进行处理很有必要
现有的用于吸附臭氧的负载型催化剂大多数以活性炭为载体，负载过渡金属的硝酸盐。由于臭氧的去除主要依靠催化剂的催化分解作用而非吸附作用，而活性炭的吸附作用远大于负载物的催化作用，致使活性炭优先吸附大量臭氧后，进一步会与臭氧发生化学反应生成一氧化碳，造成二次污染；在催化剂制备过程中，硝酸盐分解为氮氧化物，再次造成二次污染。
发明内容
本发明所要解决的技术问题是提供一种除臭氧率高、环保无污染的负载型常温除臭氧催化剂的制备方法。
本发明解决上述技术问题所采用的技术方案为：一种负载型常温除臭氧催化剂的制备方法，包括以下步骤：
(1)将含有沉淀剂的溶液匀速滴加于含有铜、锰金属盐溶液中，滴加完毕后继续搅拌2-5小时，得到沉淀物，然后进行抽滤、洗涤、干燥，在350-500℃空气气氛中焙烧2-3小时，得到除臭氧催化剂活性粉体；
(2)将步骤(1)得到的活性粉体、去离子水与粘结剂按质量比(2-3)：(13-15)：(3-4)的比例混合，并搅拌3-5小时得到浸渍液，将蜂窝状载体浸渍在浸渍液中0.5-1min，取出后吹尽残液，在100-140℃条件下烘干，得到负载型常温除臭氧催化剂。
所述的沉淀剂为氢氧化钠、氢氧化钾、氨水、碳酸氢钠、碳酸氢钾、碳酸氢铵、碳酸钠、碳酸钾和碳酸铵中的至少一种。
所述的铜、锰金属盐为氯盐、硝酸盐、硫酸盐或者醋酸盐。
所述的铜、锰金属盐与所述的沉淀剂的摩尔量之比为1：(1-2)，所述的铜、锰金属盐溶液中铜金属和锰金属摩尔比为1：(1-3)。
所述的粘结剂为硅酸钠、水玻璃、硅溶胶、铝溶胶或者磷酸盐。
所述的蜂窝状载体为蜂窝状陶瓷板，在浸渍前进行预处理，具体为经过酸液浸泡后洗净，并在200-400℃条件下烘干焙烧2-4小时。
在步骤(1)中，所述的沉淀物的干燥温度为90-120℃，干燥时长为4-6小时。
与现有技术相比，本发明的优点在于：本发明一种负载型常温除臭氧催化剂的制备方法，其以沉淀法制备活性粉体，洗涤至中性，得到铜锰氧化物粉末，焙烧不会产生污染气体；活性粉体负载于高比变面积的蜂窝状载体，大大提高了臭氧与催化剂的接触面积，使该负载型除臭氧催化剂在室温条件下，除臭氧率达到97-98％。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
具体实施例
实施例1：
分别称取0.068g的氯化锰固体与1.705g氯化铜，溶解于100mL去离子水中，混合均匀；称取1.6g氢氧化钠溶解于50mL去离子水中，将氢氧化钠溶液匀速滴加于含有金属盐的溶液中，并继续，滴加完毕后继续搅拌2小时，使反应完全，将得到的沉淀抽滤、洗涤、干燥，在马弗炉中焙烧3小时，马弗炉的设定温度为350℃，升温速率为2-8℃/min，得到除臭氧催化剂活性粉体。将活性粉体、去离子水和硅酸钠按质量比为1：7：2的比例混合，并剧烈搅拌4小时，将蜂窝状陶瓷板(蜂窝状陶瓷板先进行预处理，即经过酸液浸泡后洗净，并在200-400℃条件下烘干焙烧3小时)浸渍在上述溶液中0.5min，吹去多余液体，在100℃条件下烘干，制得负载型除臭氧催化剂。该负载型除臭氧催化剂在室温条件下，除臭氧率达到97％。
实施例2：
分别称取24.1g的三水合硝酸铜固体与35.79g的50wt％硝酸锰溶液，溶解于100mL去离子水中，混合均匀；称取27.6g碳酸钾溶解于50mL去离子水中，将碳酸钾溶液匀速滴加于含有金属盐的溶液中，并继续，滴加完毕后继续搅拌5小时，使反应完全，将得到的沉淀抽滤、洗涤、干燥，在500℃空气气氛中焙烧2小时，得到除臭氧催化剂活性粉体。将活性粉体、去离子水与水玻璃按质量比为3：14：3的比例混合，并剧烈搅拌4小时，将蜂窝状陶瓷板浸渍在上述溶液中1min，吹去多余液体，在140℃条件下烘干，制得负载型除臭氧催化剂。该负载型除臭氧催化剂在室温条件下，除臭氧率达到98％。
除上述实施例外，步骤(1)中铜、锰金属盐还可以为硫酸盐或者醋酸盐；沉淀剂还可以为氢氧化钾、氨水、碳酸氢钠、碳酸氢钾、碳酸氢铵、碳酸钠或者碳酸铵；铜、锰金属盐与沉淀剂的摩尔量之比可以为1：(1-2)内的任一值，铜、锰金属盐溶液中铜金属和锰金属摩尔比可以为1：(1-3)内的任一值；沉淀物的干燥温度为90-120℃，干燥时长为4-6小时，干燥后的沉淀物空气气氛中焙烧温度还可以为350-500℃内的任一值，焙烧时间还可以为2-3小时内的任一值；
步骤(2)中粘结剂除硅酸钠和水玻璃外，还可以为硅溶胶、铝溶胶或者磷酸盐，活性粉体、去离子水与粘结剂的混合质量比还可以为3：13：3、3：15：3、2：13：4或者2：15：4，混合后搅拌时间还可以为3小时或者5小时；蜂窝状载体浸渍时间还可以为0.5-1min内任一值，烘干温度还可以为100-140℃内任一值。
上述说明并非对本发明的限制，本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内，做出的变化、改型、添加或替换，也应属于本发明的保护范围。
Claims (7)
1.一种负载型常温除臭氧催化剂的制备方法，其特征在于包括以下步骤：
(1)将含有沉淀剂的溶液匀速滴加于含有铜、锰金属盐溶液中，滴加完毕后继续搅拌2-5小时，得到沉淀物，然后进行抽滤、洗涤、干燥，在350-500℃空气气氛中焙烧2-3小时，得到除臭氧催化剂活性粉体；
(2)将步骤(1)得到的活性粉体、去离子水与粘结剂按质量比(2-3)：(13-15)：(3-4)的比例混合，并搅拌3-5小时得到浸渍液，将蜂窝状载体浸渍在浸渍液中0.5-1min，取出后吹尽残液，在100-140℃条件下烘干，得到负载型常温除臭氧催化剂。
2.根据权利要求1所述的一种负载型常温除臭氧催化剂的制备方法，其特征在于：所述的沉淀剂为氢氧化钠、氢氧化钾、氨水、碳酸氢钠、碳酸氢钾、碳酸氢铵、碳酸钠、碳酸钾和碳酸铵中的至少一种。
3.根据权利要求1所述的一种负载型常温除臭氧催化剂的制备方法，其特征在于：所述的铜、锰金属盐为氯盐、硝酸盐、硫酸盐或者醋酸盐。
4.根据权利要求1-3中任一项所述的一种负载型常温除臭氧催化剂的制备方法，其特征在于：所述的铜、锰金属盐与所述的沉淀剂的摩尔量之比为1：(1-2)，所述的铜、锰金属盐溶液中铜金属和锰金属摩尔比为1：(1-3)。
5.根据权利要求4所述的一种负载型常温除臭氧催化剂的制备方法，其特征在于：所述的粘结剂为硅酸钠、水玻璃、硅溶胶、铝溶胶或者磷酸盐。
6.根据权利要求4所述的一种负载型常温除臭氧催化剂的制备方法，其特征在于：所述的蜂窝状载体为蜂窝状陶瓷板，在浸渍前进行预处理，具体为经过酸液浸泡后洗净，并在200-400℃条件下烘干焙烧2-4小时。
7.根据权利要求1所述的一种负载型常温除臭氧催化剂的制备方法，其特征在于：在步骤(1)中，所述的沉淀物的干燥温度为90-120℃，干燥时长为4-6小时。
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