CN110314678A - 一种臭氧催化剂及其制备方法及用于处理工业废水的方法 - Google Patents
一种臭氧催化剂及其制备方法及用于处理工业废水的方法 Download PDFInfo
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- CN110314678A CN110314678A CN201910628410.3A CN201910628410A CN110314678A CN 110314678 A CN110314678 A CN 110314678A CN 201910628410 A CN201910628410 A CN 201910628410A CN 110314678 A CN110314678 A CN 110314678A
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- ozone catalyst
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- drying
- transition metal
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- 239000002184 metal Substances 0.000 claims description 4
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010457 zeolite Substances 0.000 claims description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 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
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- 239000010949 copper Substances 0.000 claims description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
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- 238000006385 ozonation reaction Methods 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
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- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims 1
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- 238000012546 transfer Methods 0.000 abstract description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
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- 238000007639 printing Methods 0.000 description 8
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- 230000035484 reaction time Effects 0.000 description 7
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
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- 230000009467 reduction Effects 0.000 description 5
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- 230000008859 change Effects 0.000 description 3
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- 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 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 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 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
- 238000010276 construction Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical class Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 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
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/80—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 zinc, cadmium or mercury
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
本发明提出了一种臭氧催化剂及其制备方法及用于处理工业废水的方法,属于污水处理技术领域。本发明的臭氧催化剂的制备方法包括如下步骤:多孔载体置于过渡金属盐溶液中,经超声水解反应后,再过滤并干燥处理,得到负载型水合过渡金属氧化物;所述负载型水合过渡金属氧化物在控制性的还原性气氛中煅烧,使产物晶化并定量脱氧,得到负载型氧缺陷臭氧催化剂。采用上述方法制备得到的臭氧催化剂具有优良的吸收和转移氧的能力,大大提高了臭氧催化剂的催化能力。
Description
技术领域
本发明涉及污水处理领域,具体地,涉及一种臭氧催化剂及其制备方法及用于处理工业废水的方法。
背景技术
随着排放标准的日趋严苛,水体中存在一些高稳定性、难生化的有机物导致排水达标困难。经济有效地去除水中这类难降解有机污染物已成为目前水处理领域研究和工程应用的热点。臭氧具备极强的氧化性,使其能与污水中的难降解有机物发生反应,将有机物的化学键断开,由大分子降解为无色的小分子。单纯使用臭氧氧化的工艺臭氧利用率较低,对难降解有机物去除率也较低。采用催化剂催化臭氧,提高臭氧的氧化利用率,是一种应用广泛的高级氧化技术。
臭氧催化剂包括均相和非均相催化剂,非均相催化剂可以重复利用,因此具有更高的应用价值。其中,贵金属系列非均相催化剂具有较高的催 化活性及稳定性,但由于价格昂贵此类催化剂难以大规模应用。因此,开发具有高活性和高稳定性的非贵金属系列非均相催化剂成为研究热点。
非均相催化臭氧氧化的反应机理大体来说有以下三种:(1)臭氧被化学吸附到催化剂表面并形成活性基团,这些活性基团可以和不能进行化学吸附的有机物反应;(2)有机分子被化学吸附到催化剂表面,并进一步和气态或者溶液中的臭氧作用;(3)臭氧和有机分子均被化学吸附到催化剂表面,并进一步和有化学吸附能力的基团相互作用。作为非均相催化剂使用,需要金属在与氧发生作用或提供桥径作用时,其价态发生快速变化,以促进氧的快速转移,提高氧利用效率。而通常情况下,金属氧化物为氧饱和状态,金属处于其最高价态,其吸收、转移氧的能力有限,因此对臭氧的催化能力也有限。
发明内容
本发明的目的至少部分地在于提供一种臭氧催化剂及其制备方法及用于处理工业废水的方法。
根据本发明的一个方面,提供一种臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:多孔载体置于过渡金属盐溶液中,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为20℃~60℃、水解时间为0.5h~24h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为80-120oC,时间为1-2h;
(3)缺氧煅烧晶化:经干燥后的产物置于还原性气氛中煅烧,其中还原性气氛浓度用氩气稀释至5%-80%,煅烧温度为600℃~1000℃,煅烧时间为0.5h~12h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为0.5-4.5wt%,氧缺陷为5%-75%。
优选地,所述多孔载体的比表面积为40 m2/g~1000 m2/g,孔道以介孔为主。
优选地,所述多孔载体的添加量占所述过渡金属盐溶液质量的10-20 wt%。
优选地,多孔载体为活性炭、沸石、氧化铝、膨润土、陶粒中的任意一种或几种。
优选地,所述过渡金属盐溶液的质量分数为2-20 wt%。
优选地,过渡金属盐中的过渡金属为钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钼、钌、钨中的任意一种或多种。
优选地,过渡金属盐中的盐为硫酸盐、硝酸盐、高氯酸盐或氯盐中的任意一种或多种。
优选地,所述还原性气氛为氢气、氨气、甲烷或一氧化碳中的任意一种。
进一步地,本发明还提供了一种采用上述臭氧催化剂的制备方法制备得到的臭氧催化剂,以及臭氧催化剂用于处理工业废水的方法。
与现有技术相比,本发明具有以下优点:
(1)本发明所述臭氧催化剂的制备方法,采用介孔型载体和超声水解反应,水合过渡金属氧化物可以均匀生长在载体孔通道和表面,从而提高负载的均匀性、分散性和立体性,特别是当催化剂在长期应用过程中发生磨损或活性组分流失的情况下,催化剂依然能保持优良的催化活性。
(2)本发明所述臭氧催化剂的制备方法,在稀释的还原性气氛中进行高温煅烧,一方面高温煅烧能提高活性组分负载的稳固性和晶化的彻底性,并为脱氧反应创造高温条件;另一方面控制性的还原性气氛能够实现活性组分可控脱氧,定量形成氧缺陷,使所制备的催化剂具有优良的氧吸收和氧转移的能力,大大提高了催化剂的活性。
具体实施方式
以下公开内容提供了多种不同实施例或实例,以实现本发明的不同特征。
本发明中,表示原料含量的单位均基于重量以份计,单位为克,除非另外说明。另外,关于本发明的技术指标的测定方法均为本领域内使用标准方法,具体可参见最新的国家标准,除非另外说明。
另外,作为本发明中的其它原材料均指本领域内通常使用的原材料。
下面通过本发明的优选实例来进一步说明本发明,需要说明的是,下述实例仅为说明目的,并非意欲限定本发明。
实施例1
本实施例中负载型氧缺陷臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:将5g的比表面积为600m2/g的活性炭多孔载体置于50g的质量浓度为2wt%的氯化铁盐溶液中,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为20℃、水解时间为24h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为80oC,时间为1h;
(3)缺氧煅烧晶化:经干燥后的产物置于氢气还原性气氛中煅烧,其中还原性气氛体积浓度用氩气稀释至5%,煅烧温度为600℃,煅烧时间为4h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为2.3wt%,氧缺陷为75%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入1 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为21mg/L,去除率达到82.5%。
实施例2
本实施例中负载型氧缺陷臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:将10g的比表面积为40m2/g的沸石多孔载体置于50g的质量浓度为4.6wt%的过渡金属盐溶液中,其中过渡金属盐溶液是将1g硝酸铁、1.3g硝酸锰溶解于47.7ml水中构成,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为30℃、水解时间为20h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为90oC,时间为1.2h;
(3)缺氧煅烧晶化:经干燥后的产物置于甲烷还原性气氛中煅烧,其中还原性气氛体积浓度用氩气稀释至10%,煅烧温度为600℃,煅烧时间为3h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为3.5wt%,氧缺陷为18%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入1 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为9 mg/L,去除率达到92.5%。
实施例3
本实施例中负载型氧缺陷臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:将10g的比表面积为800m2/g的活性炭多孔载体置于50g的质量浓度为7.7wt%的过渡金属盐溶液中,其中过渡金属盐溶液是将1.2g氯化铁、1.2g氯化锰、1.45g氯化钨溶解于46.15ml水中构成,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为40℃、水解时间为3h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为100oC,时间为1.4h;
(3)缺氧煅烧晶化:经干燥后的产物置于甲烷还原性气氛中煅烧,其中还原性气氛体积浓度用氩气稀释至30%,煅烧温度为700℃,煅烧时间为5h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量其中负载量为2.1 wt%,氧缺陷为64%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入1 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为12 mg/L,去除率达到90%。
实施例4
本实施例中负载型氧缺陷臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:将10g的比表面积为400m2/g的膨润土多孔载体置于50g的质量浓度为11.2wt%的过渡金属盐溶液中,其中过渡金属盐溶液是将2g硝酸钴、2g硝酸镍、1.6g硝酸铬溶解于44.4ml水中构成,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为40℃、水解时间为9h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为100oC,时间为1.6h;
(3)缺氧煅烧晶化:经干燥后的产物置于一氧化碳还原性气氛中煅烧,其中还原性气氛体积浓度用氩气稀释至50%,煅烧温度为800℃,煅烧时间为8h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为4.5wt%,氧缺陷为55%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入2 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为15mg/L,去除率达到87.5%。
实施例5
本实施例中负载型氧缺陷臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:将10g的比表面积为800m2/g的活性炭多孔载体置于50g的质量浓度为16.3wt%的过渡金属盐溶液中,其中过渡金属盐溶液是将4.05g硫酸铜,4.1g硫酸锌溶解于41.85ml水中构成,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为50℃、水解时间为15h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为110oC,时间为1.8h;
(3)缺氧煅烧晶化:经干燥后的产物置于氨气还原性气氛中煅烧,其中还原性气氛体积浓度用氩气稀释至80%,煅烧温度为900℃,煅烧时间为6h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为3.2wt%,氧缺陷为22%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入1 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为8mg/L,去除率达到93.33%。
实施例6
本实施例中负载型氧缺陷臭氧催化剂的制备方法,包括如下步骤:
(1)超声水解:将10g的比表面积为1000m2/g的活性炭多孔载体置于50g的质量浓度为20wt%的过渡金属盐溶液中,其中过渡金属盐溶液是将5g硝酸钼,5g硝酸钛溶解于40ml水中构成,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为60℃、水解时间为0.5h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为120oC,时间为2h;
(3)缺氧煅烧晶化:经干燥后的产物置于甲烷还原性气氛中煅烧,其中还原性气氛体积浓度用氩气稀释至50%,煅烧温度为1000℃,煅烧时间为0.5h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为0.5wt%,氧缺陷为5%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入2 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为23mg/L,去除率达到80.83%。
对比例:与实施例5的区别仅在步骤(3)和步骤(4)中,步骤(3)经干燥后的产物不在还原性气氛中煅烧,而在常规空气中进行煅烧,煅烧时间和煅烧温度不变;步骤(4)经煅烧后的产物在空气气氛下自然冷却,得到负载型臭氧催化剂,其中负载量为3.1wt%。
性能测试:以保定某印染厂生化尾水作为处理对象,初始COD为120 mg/L,通过烧杯实验,加入1 g催化剂处理 50 ml废水,臭氧连续投加,总投加量控制为12 mg,反应时间1h。实验后COD为37mg/L,去除率仅为69.17%。
由上述实施例和对比例的测试结果可知,本发明所述负载型氧缺陷臭氧催化剂的制备方法,在稀释的还原性气氛中进行高温煅烧,能提高活性组分负载的稳固性和晶化的彻底性,同时还可以实现活性组分可控脱氧,定量形成氧缺陷,使所制备的催化剂具有优良的氧吸收和氧转移的能力,催化剂的活性。处理保定某印染厂生化尾水时,COD去除率可以高达80.83%~93.33%,远高于不经还原性气氛煅烧的催化剂的污水处理能力。
以上论述了若干实施例的部件,使得本领域的技术人员可以更好地理解本发明的各个方面。本领域技术人员应该理解,可以很容易地使用本发明作为基础来设计或更改其他的处理和结构以用于达到与本发明所介绍实施例相同的目的和/或实现相同优点。本领域技术人员也应该意识到,这种等同构造并不背离本发明的精神和范围,并且在不背离本发明的精神和范围的情况下,本文中他们可以做出多种变化、替代以及改变。
Claims (10)
1.一种臭氧催化剂的制备方法,其特征在于,包括如下步骤:
(1)超声水解:多孔载体置于过渡金属盐溶液中,经过超声水解反应后,载体表面附着生长水合过渡金属氧化物,超声水解温度为20℃~60℃、水解时间为0.5h~24h,水解过程持续机械搅拌;
(2)过滤干燥:过滤经超声水解后的混合溶液,滤出固体置于干燥箱中干燥,其中干燥温度为80-120oC,时间为1-2h;
(3)缺氧煅烧晶化:经干燥后的产物置于还原性气氛中煅烧,其中还原性气氛浓度用氩气稀释至5%-80%,煅烧温度为600℃~1000℃,煅烧时间为0.5h~12h;
(4)冷却:经煅烧后的产物在还原性气氛中自然冷却,得到负载型氧缺陷臭氧催化剂,其中负载量为0.5-4.5wt%,氧缺陷为5%-75%。
2.根据权利要求1所述的臭氧催化剂的制备方法,其特征在于,所述多孔载体的比表面积为40 m2/g~1000 m2/g,孔道以介孔为主。
3.根据权利要求1或2所述的臭氧催化剂的制备方法,其特征在于,所述多孔载体的添加量占所述过渡金属盐溶液质量的10-20 wt%。
4.根据权利要求1或2或3所述的臭氧催化剂的制备方法,其特征在于,多孔载体为活性炭、沸石、氧化铝、膨润土、陶粒中的任意一种或几种。
5.根据权利要求1所述的臭氧催化剂的制备方法,其特征在于,所述过渡金属盐溶液的质量分数为2-20 wt%。
6.根据权利要求1或5所述的臭氧催化剂的制备方法,其特征在于,过渡金属盐中的过渡金属为钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、钼、钌、钨中的任意一种或多种。
7.根据权利要求1或5或6所述的臭氧催化剂的制备方法,其特征在于,过渡金属盐中的盐为硫酸盐、硝酸盐、高氯酸盐或氯盐中的任意一种或多种。
8.根据权利要求1~7任一所述的臭氧催化剂的制备方法,其特征在于,所述还原性气氛为氢气、氨气、甲烷或一氧化碳中的任意一种。
9.一种臭氧催化剂,其特征在于,由所述权利要求1~8任一所述的制备方法制备得到。
10.一种处理工业废水的方法,其特征在于,应用权利要求9所述臭氧催化剂,对工业废水进行臭氧催化氧化处理。
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